CH403131A - Process for the preparation of water-soluble disazo dyes - Google Patents

Description

  

  Process for the preparation of water-soluble disazo dyes The invention relates to a process for the preparation of water-soluble disazo dyes of the formula
EMI0001.0003
    wherein R1 and R5 are optionally substituted acyl radicals or radicals of azinylating agents which contain at least one exchangeable halogen atom,

         R2 and R4 denote optionally substituted phenylene and R3 denote the radical of an optionally substituted diphenyl, where R1 and R5 or R2 and R4 can be identical to or different from one another.



  The procedure consists in making 1 mole of a compound of formula
EMI0001.0023
    with 2 moles of an acylating agent or azinyla- ying agent or

   condensed with 1 mol of two different compounds of this type, the radicals R1, R2, R3, R4 and R5 being selected so that the final dye has the number of solubilizing groups necessary for solubility in water.



  The disazo dye of the formula (11) used as the starting dye can be added, for example, by coupling the tetrazo compound from 1 mol of an optionally substituted 4,4'-diamino-1,1'-diphenyl with 1 mol of two in the para position an amino group coupling,

   optionally substituted aminobenzenes or derivatives thereof which are capable of being coupled and which can be converted into the amino compound, it also being possible to use 2 mol of an identical compound.



  As diamino compounds which can be used for the radical R3, for example: 4,4'-diamino-2,2'-dimethyl-1,1'-diphenyl, 4,4'-diamino-1,1'- diphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-diphenyl 5-sulfonic acid, 4,4 = 1) iamino-2,2'-dimethyl-1,1'-diphenyl-6 = sulfonic acid, 4,4'-diamino-3,3'-dimethyl-1,1'-diphenyl-6,6'-disulfonic acid, 4,4'-diamino-1,1'-diphenyl-2,2'-disulfonic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-disulfonic acid,

       '- -4,4'-diamino-l, l'-diphenyl-2,2', 5,5'-tetra sulfonic acid, 4,4 'diamino-3,3'-diethyl 1,1'-diphenyl 6,6'-disulfonic acid, 4,4'-diamino-3,3'-dimethoxy-1,1'-diphenyl-6,6'-disulfonic acid, 4,4'-diamino-1,1'-diphenyl-3 , 3'-dicarboxylic acid, 4,4'-diamino-3,3'-dimethoxy-1,1'-diphenyl, 4,4'-diamino-3,3'-dimethyl-1,1'-diphenyl, 4,4 '-Diamino-1,1' - (Ephenyl "6,6'-sulfone-3,3'-disulfonic acid, - 4,4'-diamino-3,3'-diethyl-1,

  1'-diphenyl, 4,4'-diamino-1,1'-diphenyl-3,3'-dihydroxydiacetic acid.



  Important aminobenzenes that correspond to the radicals R2 and R4 are, for. B. the following: aminobenzene, 1-amino-2- or -3-methylbenzene, 1-amino-3-acetyl-aminobenzene, 1-amino-2,5-dimethoxybenzene, 1-amino-5-methyl-2-methoxybenzene , 1-amino-3-propionyl or

       butyrylaminobenzene, 1,3-diaminobenzene, 1-amino-2,5-dimethylbenzene, 1-amina-2,3-tetramethylene benzene. Functional derivatives of an organic acid are preferably used to introduce the radicals R1 and R5, such as the halides, preferably the chlorides and bromides, and the anhydrides of the optionally substituted fatty acids having 1 to 30 carbon atoms, e.g. B.



       Acetyl chloride, acetic anhydride, maleic anhydride, isovaleric acid chloride, 2-ethylcaproic acid chloride, capric acid chloride, lauric acid chloride, oleic acid chloride, palmitic acid chloride, stearic acid anhydride and chloride, phenylacetic acid chloride and 2,4,5-trichlorophenoxyacetic acid chloride, preferably the chlorophenoxyacetic acid chloride, the halides

      and the anhydrides of the optionally substituted mono- or binuclear aromatic carboxylic acids, preferably of the benzene or naphthalene series and of the arylalkyl or cycloalkylcarboxylic acids, eg. B.



       4-tert-butylbenzoic acid chloride, butylglycoloxyacetic acid chloride, phenoxy- and cresoxyacetic acid chlorides, benzoic acid chloride, mono- and dichlorobenzoic acid chlorides and cyclohexylcarboxylic acid chloride, furthermore the halides of the alkanesulfonic acids with 1 to 30 carbon atoms, the optionally substituted aromatic sulfonyl series, or preferably the aromatic sulfonic acids

      and the haloformic acid esters of optionally substituted aliphatic alcohols having 1 to 20 carbon atoms, of cycloaliphatic and arylaliphatic alcohols and of optionally substituted phenols and naphthols, for example the chloroformic acid esters of ethyl, amyl, hexyl, octyl, decyl,

            Lauryl or cetyl alcohol, benzyl or cyclohexyl alcohol, hydroxybenzene, 4-octyl or 4-cyclohexyl - 1-hydroxybenzen, and especially ethylene glycol monoethyl, -butyl, -hexyl-, -octyl- or phenyl ethers, as well as diethylene glycol monomethyl, butyl or phenyl ethers,

       as well as the functional derivatives of chloroacetic acid, bromoacetic acid, ss-chloro and ss-bromopropionic acid, propiolic acid, acrylic acid, methacrylic acid, a-chloro, ss-chloro, a-bromo and ss-bromo acrylic acid, a, ss- and ss, ss-dichloro or dibromoacrylic acid, trichloro or tribromoacrylic acid, crotonic acid, a-,

       ss-, γ-chlorocrotonic acid, <I> a-, </I> ss-, <I> y </I> bromocrotonic acid, α-, ß-dichlorocrotonic acid, maleic acid, monochloro and monobromomaleic acid, dichloro and dibromaleic acid, fumaric acid , Monochloro and monobromofumaric acid, dichloro and dibromofumaric acid, fumaric acid monoester,

            Dichloro and dibromosuccinic acid.



  As residues of azinylating agents, which min least one. Contain exchangeable halogen atom, come into consideration: z. B. residues of tetrameric chlorine or cyanogen bromide, cyanuric chloride or bromide, primary or secondary condensation products of the cyanuric halides of the composition
EMI0002.0129
    where y is the optionally further substituted radical of a primary or secondary aliphatic, alicyclic,

      aromatic or heterocyclic amine, an aliphatic, alicyclic, aromatic or heterocyclic hydroxy or thiol compound, but in particular the remainder of aniline, its alkyl and sulfonic acid or carboxylic acid derivatives, of lower mono- and dialkylamines and the remainder of ammonia and z a Halogen atom or a radical such as y, furthermore 2.4,

  6-Trichloropyrimidine and 2,4,6-tribromopyrimidine, and their derivatives, which carry, for example, the following substituents in the 5-position: methyl, ethyl, optionally substituted carboxylic acid or sulfonic acid amide, carboxylic acid methyl or ethyl ester, acyl , e.g. Benzoyl, alkylene, e.g.

   B. allyl, chlorovinyl, substituted alkyl, e.g. B. carboxymethyl, chloro- or bromomethyl, and a methylene group between tween two pyrimidine nuclei, 2,4,5,6-tetrachloro or -Tetrabromopyrimidin, 2,5 = dichloro- or -dibromopyrimidine-4-carboxylic acid ethyl ester, 2,4 , 5-trichloropyrimidine, the 4- or

       5-carboxamide or sulfonic acid amide derivatives of 2,6-dichloro- or dibromopyrimidine, 2,5,6-trichloro-4-methylpyrimidine, 2,4-dichloro-5-chloromethyl-6-methylpyrimidine and 2,6-dichloro -4-trichloromethylpyrimidine. The acyl radicals R and / or R5 can also be radicals of α-sulfatopropionic acid or α- (p-toluenesulfonyl'-oxy) propionic acid.



  When introducing the acyl radical, the procedure is as a rule that the dye to be acylated in an aqueous medium, possibly with the addition of an organic solvent, such as. B. acetone, dioxane, and the acylating agent at lower or higher temperature, optionally in the presence of acid-binding agents, such as sodium hydroxide, sodium carbonate, sodium bicarbonate, calcium hydroxide, calcium carbonate or pyridine, which can also be Ka catalyst, is added.



  In many cases, the free organic acid, optionally a salt of the organic acid, can be used, the condensation with the dye in the presence of dehydrating agents, such as. B. Oleum, takes place.



  The introduction of a cyanuric residue is best done in an aqueous medium at around 0 C and in a weakly acidic reaction, e.g. B. at pH values between 3 and 5, made. The cyanuric halide is used as such in solid form or dissolved in an organic solvent, e.g. B. in acetone.

   For the primary condensation products of a cyanuric halide, it is best to choose a temperature of 30 to 60 C and a pH of 4 to 6, for the secondary condensation products a temperature of 70-100 C and a pH of 4 to 10, while for the di-, tri- and tetrahalopyrimidines temperatures between 40 and 100 C are most suitable, in the case of the cyanuric halides,

      whose primary condensation products and the di-, tri- or tetrahalopyrimidines can exchange the remaining exchangeable halogen atoms for optionally substituted amino, hydroxyl or thiol groups.



  After the condensation has ended, the finished dyestuff is advantageously salted out with sodium or potassium chloride or precipitated with acid from its optionally previously neutralized solution or suspension, then filtered off with suction, washed and dried.



  The dyes obtainable according to the invention are suitable, depending on their composition, for dyeing, padding and printing fibers of animal origin, e.g. B. wool, silk, synthetic polyamide fibers, e.g. B. nylon, leather, cellulose fibers, z. B. cotton, linen and regenerated cellulose fibers, e.g. B. Viscosereyon, Kupferreyon, rayon, as well as mixtures and or structures of these fibers.

   The optimal application conditions differ depending on the type of fiber and the dyes used. Animal fibers and synthetic polyamide fibers are preferably used in an acidic, neutral or weakly alkaline medium, e.g. B. in the presence of acetic acid, formic acid, sulfuric acid, ammonia sulfate, sodium metaphosphate, ge optionally in the presence of leveling agents, eg. B.

         polyoxyethylated fatty amines or mixtures thereof with alkyl polyglycol ethers, dye or be printed, with dyes which contain easily removable substituents or GC multiple bonds easily capable of addition as anions, with suitable aftertreatment, preferably in the presence of an acid-binding agent, with the fiber a chemical Connection. In the latter case, at the end of the dyeing process, the bath is cleaned by adding small amounts of an alkaline agent, e.g. B.

   Ammonia, sodium bicarbonate, soda etc. or compounds which react alkaline in the heat, e.g. B. hexamethylene tetramine, urea, blunted to a neutral or weakly alkaline reaction. This is followed by thorough rinsing and, if necessary, acidified with a little acetic acid.



  Dyeing, padding and printing with dyes which have sufficient substantivity for cellulose fibers can be carried out in the usual way in a neutral to slightly alkaline medium.

   in the presence of electrolytes such as sodium chloride, sodium sulfate, etc., take place. If the dyes obtainable according to the invention have easily cleavable substituents as anions or GC multiple bonds which are easily capable of addition, they can be fixed to the cellulose fiber by chemical bonding. In this case, the dyeing, padding and printing or fixing of the dyes is advantageously carried out in an alkaline medium, e.g.

   B. in. Presence of sodium bicarbonate, sodium carbonate, caustic soda, potassium hydroxide, sodium metasilicate, sodium borate, trisodium phosphate, ammonia, etc. To avoid reduction phenomena who the when dyeing, padding or printing the fibers often with advantage mild oxidizing agents such. B. 1-nitrobenzene-3-sulfonic acid sodium added.

   In the case of cellulose fibers, the dyes are usually fixed in the heat. Some of the dyes, depending on the reactivity of the reactive groups, even at low tempera tures, z. B. at 20-40 C, colored or fixed who the. At the end it is rinsed and / or soaped, if necessary using higher temperatures, with synthetic detergents, such as.

   B. alkylarylsulfonates, nairium laurylsulfonate, sodium lauryl polyglycal ether sulfate and mono- and di-alkylphenol polyglycol ethers are used.

   The dyeings and prints on cellulose are distinguished in particular by excellent wet fastness properties, the dyeings on wool by excellent light, perspiration, washing, seawater and milled fastness, as well as fastness to dry cleaning and good leveling power.



  In the example, the parts are parts by weight, the percentages are percentages by weight, and the temperatures are given in degrees Celsius. <I> Example </I> 30 parts of the dye which can be obtained by tetrazotizing 3,3'-ilimethyl-4,4'-diamino-1,1'-diphenyl-6,6'-disulfonic acid and twice Coupling with 1-methyl-3-aminobenzene in weakly acidic solution is dissolved in 2400 parts of water and 450 parts of acetone.

   200 parts of sodium bicarbonate are added, the mixture is cooled to 0-5 and 100 parts of monochloroacetic acid chloride are added dropwise over the course of 2 hours. As soon as no free amine can be detected, the new dye which has now precipitated is filtered off, washed with 100 parts of 5% sodium chloride solution and dried at 40 in a vacuum.



  After grinding, an orange-colored powder is obtained which, from an acetic acid bath, to which a wetting agent is optionally added, gives an orange dye on wool with excellent wet fastness properties and good light fastness.

 

Claims (1)

PATENT CLAIM Process for the preparation of water-soluble disazo dyes of the formula EMI0004.0022 wherein R1 and R5 optionally substituted acyl radicals or radicals of azinyherungsmittel which contain at least one exchangeable halogen atom, R2 and R4 are optionally substituted phenylene and R3 is the radical of an optionally substituted diphenyl, where R1 and R5 or R2 and R4 can be identical to or different from one another, characterized in that 1 mol of a compound of the formula EMI0004.0042 with 2 moles of an acylating agent or azinyla- ying agent or condensed with 1 mol of two different compounds of this type, the radicals R1, R2, R3, R4 and R5 being selected so that the final dye has the number of solubilizing groups necessary for solubility in water.