CH523955A - Basic azo dyes - Google Patents

Abstract

Basic azo dyes have formula: (where D is opt. substd. aromatic-carbocyclic or aromatic-heterocyclic; R1 is CN, acyl ro carboxylic acid; R2 is unsubstd. alkyl or opt. subst. aryl or opt. substd. heterocyclic radical, or -NR3R4; R3 and Rj are H or opt. substd. alkyl or aryl, or together with the N atom form a ring; Y1 is a divalent gp.; K+ is opt. substd., etherified hydroxylammonium gp.; and A-1 is anion. Dyes can be used for dyeing or printing acrylonitrile textile material.

Description

  

  
 



  Process for the preparation of sulfonic acid group-free azo compounds
The invention relates to a process for the preparation of new basic azo compounds of the formula which are free from sulfonic acid groups
EMI1.1
 wherein D is an optionally substituted aromatic-heterocyclic radical,
R, the cyano group, an acyl radical or a carboxylic acid ester radical
R2 is an unsubstituted alkyl radical or an optionally substituted aryl radical or an optionally substituted heterocyclic radical or a group of the formula
EMI1.2
 R3 and R4 each represent a hydrogen atom or an optionally substituted alkyl or aryl radical.

   or can form a ring together with -N-, Yl is a divalent bridge member, K is an optionally substituted, etherified hydroxylamminium group, and
A mean an anion.



   Interesting compounds correspond to the formula
EMI1.3
 wherein R 'and R'2 each represent an optionally substituted alkyl or cycloalkyl radical,
R'3 denotes an optionally substituted hydrocarbon radical, and R 'and R'2 together with the N atom can form a heterocycle and D, Rl, R ,, Y1 and A have the meanings given above, or of the formula
EMI1.4
 where R "2 denotes an optionally substituted alkyl or cycloalkyl radical and D, Ra, R2, Y, R'l, R'3 and A have the meanings given above.



   The new basic azo compounds of the formula (1) are prepared when a compound of the formula
EMI2.1
 where A denotes a radical which can be converted into an anion, reacted with an optionally substituted etherified hydroxylamine.



   The azo compounds of the formula (II) can be obtained by combining a compound of the formula (VI) with a compound of the formula
EMI2.2
 implements.



   The new compounds are used for dyeing or printing fibers, threads or textiles made therefrom, which consist of or contain acrylonitrile polymers or copolymers.



   You can also dye or print synthetic polyamides or synthetic polyesters which have been modified by acidic groups. Such polyamides are known, for example, from Belgian patent specification 706 104.



  The corresponding polyesters are known from US Pat. No. 3,379,723.



   The compounds are also used to color plastics, leather and paper. It is particularly advantageous to dye in an aqueous, neutral or acidic medium at temperatures from 60 ° C. to the boiling point or at temperatures above 100 ° C. under pressure. Level dyeings with good lightfastness and good wetfastnesses are obtained.



   Those compounds which have good solubility in organic solvents are also suitable for coloring natural plastic compositions or dissolved or undissolved plastic, synthetic resin or natural resin compositions. Some of the new connections can, for. B.



  can be used for dyeing cotton, wool, silk, regenerated cellulose and synthetic polyamides. It has been shown that mixtures of two or more of the new compounds or mixtures with other cationic dyes can also advantageously be used.



   In the compounds of the formula (1), the anion A can be exchanged for other anions, e.g. B. with the help of an ion exchanger or by reacting with salts or acids, optionally in several stages, e.g. B. via the hydroxide.



   Anion A is understood to mean both organic and inorganic ions, e.g. B. halogen such as chlorine, bromine, iodine or hydroxide, carbonate, bicarbonate, methyl sulfate, sulfate, disulfate, perchlorate, phosphate, phosphotungsten molybdate, benzenesulfonate or naphthalenesulfonate, 4-chlorobenzenesulfonate -, amidosulfonate, oxalate, acetate, maleate, lactate, propionate, citrate, methanesulfonate, chloroacetate or benzoate ions or complex anions, such as. B. of zinc chloride double salts.



   It is assumed that the compounds of the formula (1) are in a tautomeric state represented by the formulas
EMI2.3
 is marked.



   Particularly good compounds are obtained when R, the cyano group and R2 the methyl or ethyl radical or an aryl radical, e.g. B. mean a phenyl radical.



   The compounds of the formula (1) are preferably free from water-solubilizing groups, in any case free from sulfonic acid groups.



   Halogen is in any case to be understood as meaning bromine, fluorine or iodine, but especially chlorine.



   The radicals R3 and R4 and R'I to R'3 can denote an optionally substituted, preferably low molecular weight, straight-chain or branched alkyl radical having, for example, 1 to 6 and advantageously 1 to 4 carbon atoms.



  If these radicals are substituted, they contain, in particular, a hydroxyl group, a halogen atom, the cyano or an acyl group; Alkyl can for such cases for an aralkyl, e.g. B. stand a benzyl radical.



   R2 advantageously represents an unsubstituted alkyl radical with, for example, 1 to 6 carbon atoms or an optionally substituted aryl radical. The alkyl radicals can be straight-chain or branched.



   Cycloalkyl radicals are advantageously cyclohexyl radicals which can be substituted by alkyl or alkoxy groups or halogen.



   Aryl radicals mainly represent optionally substituted phenyl radicals; but they can also stand for naphthyl radicals.



   The radicals R 'and R'2 can form a heterocycle together with the adjacent N atom, for example a pyrrolidine, piperidine, morpholine, aziridine or piperazine ring.



   Heterocyclic radicals, such as. B. the radicals D and / or R2 can represent 5- or 6-membered ring systems to which cycloaliphatic, heterocyclic or aromatic rings can optionally be fused; you can z. B.



  a pyridine, quinoline, piperidine, isoquinoline, tetrahydroquinoline, thiazole, benzthiazole, thiadiazole, indazole, imidazole, pyrrole, indole, oxazole, isoxazole or pyrazoline ring and so on.



   Aromatic radicals D advantageously belong to the benzene or naphthalene series.



   Divalent bridge members Y1 can be optionally substituted alkylene radicals having, for example, 1 to 6 carbon atoms, where the alkylene radicals can be straight-chain or branched or interrupted by heteroatoms or heteroatom groups, e.g. B. by
EMI3.1
 wherein R6 denotes a hydrogen atom or an optionally substituted hydrocarbon radical.



   As residues A, e.g. B. acid residues of esters, those of the hydrohalic acids are preferred; A preferably represents chlorine or bromine. Further acid residues A are, for example, those of sulfuric acid, a sulfonic acid or hydrogen sulfide.



   Preferred acyl radicals, preferably water-solubilizing acrylic radicals, correspond to the formula R7-X or R8-X2 in which R7 is an optionally substituted hydrocarbon radical which may contain heteroatoms,
R8 is a hydrogen atom or an optionally substituted hydrocarbon radical which may contain heteroatoms, X -O-CO- or -SO2-,
EMI3.2
 mean.



   Hydrocarbon radicals are, in particular, optionally substituted alkyl, cyclohexyl, phenyl or naphthyl radicals.



   Preferred etherified hydroxylamines are, for example, the following:
EMI3.3
 or
EMI3.4

The reaction of a compound of the formula (VI) with an optionally substituted, etherified hydroxylamine. takes place preferably in an organic solvent and at temperatures from -50 "C to +250 C, advantageously at -10" to +120 "C.



   The reaction can be carried out in an aqueous medium, optionally with the addition of an organic solvent or else entirely without a solvent, at the temperatures mentioned.



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



  example 1
17.25 parts of l-amino-2-nitro4-chlorobenzene are diazotized in a known manner. 21.3 parts of 1- (2'-hydroxy) ethyl-2-keto-3-cyano4-methyl-6-hydroxy-1s2-dihydropyridine, dissolved in 50 parts of glacial acetic acid, are added dropwise to the hydrochloric acid diazo solution at 0 over the course of one hour . At the same time, 200 parts of a 70% aqueous solution of crystallized sodium acetate are added dropwise. The dried dye is then dissolved in a mixture consisting of 700 parts of toluene and 70 parts of dimethylformamide.

  This solution is mixed with 13.2 parts of thionyl chloride over the course of one hour and the reaction mass is heated to 105. The mixture is then cooled to 40 and the solution is mixed with 13.7 parts of N-methoxy-N-methyl-2-hydroxy-ethylamine and heated to 105 for 5 hours. The precipitated dye is collected on a filter, dried and purified by recrystallization.



   The new dye is readily soluble in water and can be used to dye polyacrylonitrile in real greenish yellow shades.



   Very similar, equally good dyes are obtained if, in Example 1, the 17.25 parts of l-amino-2-nitro-4-chlorobenzene are replaced by the equivalent amount of l-amino-4-nitro-2-chlorobenzene or 1-amino-2 -nitro4-methylbenzene or l-aminobenzene-4-sulfodimethylamide or 1-aminobenzene-4-acetylbenzene or 4-aminobenzoic acid ethyl ester or l-amino-2,5-dichlorobenzene or 1-amino-2,4-dinitrobenzene or by adding 13.7 parts N-methoxy-N-methyl-2-hydroxy-ethylamine replaced by the equivalent amount of N-methoxy-n-methylbenzylamine, triethylhydroxylamine, N-ethoxy-N-ethyl-2-hydroxy-ethylamine, N-methoxydibutylamine.



  Staining instructions
20 parts of the dye from Example 1 are mixed with 80 parts of dextrin in a ball mill for 48 hours; 1 part of the preparation thus obtained is made into a paste with 1 part 400 / acetic acid, 200 parts of demineralized water are poured over the paste and briefly boiled.



  It is diluted with 7000 parts of demineralized water, 2 parts of glacial acetic acid are added and at 60, 100 parts of polyacrylonitrile fabric are added to the bath. The material can be pretreated beforehand for 10 to 15 minutes at 60 in a bath consisting of 8000 parts of water and 2 parts of glacial acetic acid.



   The mixture is heated to 98-100 within 30 minutes, boiled for 1 hour and rinsed. A greenish yellow dyeing with good lightfastness and good wetfastnesses is obtained.



   If the 17.25 parts of l-amino-2-nitro-4-chlorobenzene in Example 1 are replaced by an equivalent amount of the amines mentioned below, quaternary dyes with equally good properties are obtained. The dyes obtained give yellow to reddish yellow dyeings on polyacrylonitrile.



     
1-amino-2-nitro4-methylbenzene
1-amino-4-benzoylaminobenzene
1-amino-4'-chlorodiphenyl ether
1-Amino-4-sulfonic acid dimethylamide
1-amino-2-chlorobenzene, 1-amino-4-chlorobenzene,
1-amino-3-chlorobenzene,
1-amino-2,5-dichlorobenzene,
1-amino-3,4-dichlorobenzene,
1-amino-2-bromobenzene,
1-amino-3-bromobenzene,
1-amino-2,4,6-tribromobenzene,
1-amino-2,4,6-trichlorobenzene,
1-amino-2-methoxybenzene,
1-amino-2-methylbenzene, l-amino-3-methylbenzene,
1-amino4-methylbenzene,

   l-amino-2,5-dimethylbenzene,
1-Amino-2-methoxybenzene-5-sulfonic acid amide,
1-amino-4-nitrobenzene, 1-amino-3-nitrobenzene,
I-aminobenzene,
1-amino-2-methoxy-4-nitrobenzene,
I-amino-2-methoxy-5-nitrobenzene,
1-amino-3-chloro-4-methoxybenzene,
1 -Amino4-acetylaminobenzene,
1-amino-4-methoxybenzene,
I -Amino4-ethoxybenzene,
I-amino-2,6-dichloro-4-nitrobenzene,
1-amino-2,4,5-trichlorobenzene,
4-Amino-4-chloro-1,1'-diphenyl ether.



  Example 2
12.75 parts of 1-amino-2-chlorobenzene are dissolved in a mixture consisting of 250 parts of water and 40 parts of 300 / above hydrochloric acid and diazotized at 0 in the usual way with 6.9 parts of sodium nitrite. A solution consisting of 1- (4-ethyl) -phenyl-2-keto-3-cyano-4-methyl-2 ", 6-dihydroxy-1, Add dropwise 2-dihydropyridine in 150 parts of glacial acetic acid and stir until the coupling is complete.



  The dyestuff which has separated out in crystallized form is filtered off and purified by recrystallization.



   40.8 parts of this dye are dissolved in 300 parts of pyridine and 22 parts of 4-methylbenzenesulfonic acid chloride are added to this solution at 10. After 7 hours of cooling at 10, the esterified dye is precipitated by dilution with 1500 parts of water, filtered off and dried.



  11.3 parts of dimethylaminobenzene and 6.5 parts of trimethylhydroxylamine are refluxed for 8 hours.

 

  The quaternary dye which precipitated on cooling is collected on a filter and washed out with chloroform.



   It dyes fibers made of polyacrylonitrile and polyvinyliclcyanide in greenish yellow shades with excellent fastness properties.



   Similar, also yellow dyes are obtained if, instead of trimethylhydroxylamine, triethylhydroxylamine, N-methoxy-N-methyl- (2'-hydroxy) -ethylamine, N-methoxy-N- (2 "-hydroxySäthylA2" -hydroxyl) - ethylamine used.



   The coupling component used in this example can be prepared by condensation of Cyanessigsäure4- (2'-hydroxy) -äthylphenylamid with acetoacetate in the presence of a secondary amine, such as. B. piperidine.

 

Claims (1)

PATENT CLAIM Process for the preparation of sulfonic acid group-free basic azo compounds of the formula EMI4.1 wherein D is an optionally substituted aromatic-carbocyclic or aromatic-heterocyclic radical, R, the cyano group, an acyl radical or a carboxylic acid ester radical, R2 is an unsubstituted alkyl radical or an optionally substituted aryl radical or an optionally substituted heterocyclic radical or a group of the formula EMI4.2 R3 and R4 each represent a hydrogen atom or an optionally substituted alkyl or aryl radical, or can form a ring together with -N-, Y is a divalent bridge member, K is an optionally substituted, etherified hydroxylammonium group and A is an anion, characterized in that that you can get a compound of the formula EMI5.1 in which A is a radical which can be converted into an anion, is reacted with an optionally substituted, etherified hydroxylamine. SUBCLAIMS 1. Process according to claim I for the preparation of compounds of the formula EMI5.2 wherein R 'and R'2 each represent an optionally substituted alkyl or cycloalkyl radical, and R'3 is an optionally substituted hydrocarbon radical, and R 'and R'2 can form a heterocycle together with the N atom. 2. The method according to claim 1, characterized in that the anion A is replaced by another anion. PATENT CLAIM II Use of the dyes produced by the process according to claim I for dyeing paper.