Heterocyclyl-azo-phenyl dyes having a cationic group linked through a branched alkylene chain to the nitrogen atom of the coupling component radical
This application is a continuation-in-part of application Ser. No. 421,018, filed Dec. 1973 and now abandoned, which in turn is a continuation-in-part of application Ser. No. 262,067, filed June 12th, 1972 and now abandoned. 
    
    
     The present invention relates to new basic azo dyes which are free from water-solubilizing groups. 
     The invention provides compounds of formula I, ##STR2## in which R 1  signifies a substituted thiazole, thiadiazole, isothiazole, oxadiazole or thiophene radical, 
     R 2  signifies hydrogen or an optionally, substituted hydrocarbon radical, 
     R 3  signifies hydrogen or an optionally substituted alkyl radical, 
     R 4  signifies hydrogen or an alkyl radical which is unsubstituted or substituted by an aryl radical, 
     K.sup.⊕ signifies an ammonium, cycloimmonium, hydrazinium, aminoxide or optionally substituted etherfied hydroxyammonium group, 
     A n ⊖ signifies an anion, 
     n signifies 1, 2 or 3, and the ring B is unsubstituted or monosubstituted, provided that at least one of R 3  and R 4  is other than hydrogen, and provided that the molecule does not contain a water-solubilizing group. 
     Preferred significances for R 1  include 4-phenyl-thiadiazole-(2)-,5-phenylthiadiazole-(2),3-phenylthiadiazole-(5)-,3-phenyloxadiazole-(5), 3-chlorothiadiazole-(5), 3-ethylmercaptothiadiazole-(5), 3-ethylsulfonylthiadiazole-(5), 5-nitrothiazole-(2),5-cyanothiazole-(2), 3-nitro-5-acetylthiophene-(2),3-phenyl-4-cyanoisothiazole-(2) and 5-phenyl-4-cyanoisothiazole, and such radicals having substituents on the phenyl radical. 
     Preferred hydrocarbon radicals for R 2  and elsewhere are optionally substituted alkyl, cycloalkyl, phenyl and naphthyl radicals. 
     Preferred alkyl radicals for R 3  have straight or branched chains of 1 to 6, especially 1 to 4, carbon atoms. Preferred substituents for such radicals are hydroxyl, halogen and cyano, or an aryl group which forms an aralkyl radical, e.g. benzyl. 
     Preferred alkyl radicals for R 4  have straight or branched chains of 1 to 6, especially 1 to 4, carbon atoms. The preferred aryl substituent is phenyl. 
     Preferred significances for K.sup.⊕ include, ##STR3## in which formulae III to VII R 6  and R 7  each independently signifies an optionally substituted alkyl or cycloalkyl radical, 
     R 8  and R 9  each independently signifies a hydrogen atom or an optionally substituted alkyl or cycloalkyl radical, 
     R 10  signifies an optionally substituted hydrocarbon radical, 
     R 11  signifies an optionally substituted hydrocarbon radical or a radical of formula L, ##STR4## in which R 1  to R 4  and ring B are as defined above, 
     R 12  signifies an optionally substituted alkyl or cycloalkyl radical, 
     R 13  signifies an optionally substituted alkyl or cycloalkyl radical, 
     R 14  signifies an amino group or an optionally substituted hydrocarbon radical, 
     R 15  signifies an optionally substituted hydrocarbon radical, 
     Z signifies a carbon or nitrogen atom, and 
     R 6  with R 7 , R 6  with R 8 , R 7  with R 9 , R 10  with R 11 , R 11  with R 12 , R 10  with R 12  or R 10  with R 11  and R 12  each independently may together with the N atom vicinal to these substituents, form a heterocycle, and 
     the group of formula VI is the radical of a multimembered preferably five or six-membered, saturated or partly saturated ring which may be further substituted, and the group of formula VII signifies the radical of a multimembered, preferably five-or six-membered, unsaturated ring which may be further substituted. 
     Preferred heterocycles formed from R 6  and R 7  or R 10  or R 11  jointly with the vicinal N⊕ atom are pyrrolidine, piperidine, morpholine, aziridine and piperazine rings. 
     When the radicals R 10 , R 11  and R 12  together with the vicinal N atom form a heterocycle, it is suitably a group of the formula ##STR5## or a pyridinium radical. 
     The group of formula VII may have cycloaliphatic, heterocyclic or aromatic rings thereon. It may therefore signify, for example, a pyridine, quinoline, piperidine, pyrrolidine, morpholine, aziridine, piperazine, isoquinoline, tetrahydroquinoline, pyrazole, triazole, triazine, pyridazine, imidazole, pyrimidine, thiazole, benzothiazole, thiadiazole, indazole, pyrrole, indole, oxazole, iso-oxazole, pyrazoline, thiophene or tetrazole ring. 
     Suitable heterocycles formed by R 6  together with R 8  and the radical R 7  together with R 9  and the N atoms vicinal to these substituents include pyrazolidine, pyridazine or pyrazoline rings, for instance trimethylenepyrazolidine tetramethylenepyrazoline. 
     Examples of preferred etherified hydroxylamines are ##STR6## 
     Preferred alkyl radicals for R 6  to R 9 , R 12  and R 13  are the same as for R 3 . Preferred cycloalkyl radicals are cyclohexyl radicals which may be substituted by alkyl or alkoxy groups or by halogen. 
     &#34;Halogen&#34; as used herein signifies bromine, fluorine, iodine or, preferably, chlorine. 
     As used herein &#34;aryl&#34; preferably signifies naphthyl or, especially, phenyl. 
     The anion A n ⊖ may be an organic or inorganic ion. The significance of A n ⊖ is not critical, provided it does not affect the colour of the compounds, i.e. preferably it is non-chromophoric. Anions conventionally used in basic dyes may be used, for example chloride, bromine, iodide, or a hydroxide, carbonate, bicarbonate, methylsulfate, sulphate, bisulphate, perchlorate, phosphate, phosphorous tungstic molybdate, borate, benzenesulphonate, 4-methylbenzenesulphonate, naphthalenesulphonate, 4-chlorobenzenesulphonate, amidosulphonate, oxalate, acetate, maleinate, malate, lactate, propionate, citrate, methanesulphonate, chloroacetate, adipate and benzoate ions or complex anions such as that of zinc chloride double salts. 
     All the radicals of aromatic character, in particular the aromatic carbocylic and aromatic heterocyclic radicals, e.g. aryl radicals such as phenyl, naphthyl, tetrahydronaphthyl, and pyridyl, quinolyl and tetrahydroquinolyl radicals, may bear substituents, that is to say non-water-solubilizing substituents, for example halogen atoms, nitro, amino, cyano, thiocyano, hydroxyl, alkyl, alkoxy, trifluoroalkyl, trichloroalkyl, phenyl, phenoxy, alkylamino, dialkylamino, phenylamino, acyl, acyloxy and acylamino groups, e.g. acetylamino, benzoylamino, and alkylsulphonyl, arylsulphonyl, sulphonic acid amide (sulfamoyl), sulphonic acid alkyl amide (alkylsulfamoyl), sulphonic acid dialkyl amide (dialkylsulfamoyl), sulphonic acid arylamide (arylsulfamoyl) groups and arylazo, e.g. phenylazo and diphenylazo. 
     Especially preferred compounds of formula I are those of formula Ia. ##STR7## in which R 1  &#39; signifies 3-phenylthiadiazole-(5), 5-phenylthiadiazole-(2),4-phenylthiadiazole-(3), 3-phenyloxadiazole-(5), 3-chlorothiadiazole-(5), 3-ethylmercaptothiadiazole-(5), 3ethylsulfonylthiadiazole-(5), 5-nitrothiazole-(2), 5-cyanothiazole-(2), 3-nitro-5-acetylthiophene-(2), 3-phenyl-4-cyanoisothiazole-(2) or 5-phenyl-4-cyanoisothiazole, 
     R 2  &#39; signifies methyl, ethyl, propyl, butyl or benzyl, 
     R 3  &#39; and R 4  &#39; independently signify hydrogen or alkyl of 1 to 4 carbon atoms, provided one of R 3  &#39; and R 4  &#39; is other than hydrogen, 
     R 17  signifies hydrogen, halogen, methyl, ethyl or methoxy, 
     K signifies a radical of the formula ##STR8## in which R x , R y  and R z  independently signify alkyl of 1 to 4 carbon atoms, which may be substituted by hydroxyl, --CONH 2 , cyano or phenyl, and one of R x , R y  and R z  may signify amino or two of R x , R y  and R z , together with the nitrogen atom, signify a ring which is ##STR9## or all of R x , R y  and R z  together with the nitrogen atom signify ##STR10## in which R w  signifies hydrogen or alkyl of 1 to 4 carbon atoms, or a radical of the formula ##STR11## in which Z signifies a carbon or nitrogen atom, 
     R v  signifies an alkyl radical of 1 to 4 carbon atoms, and the ring is unsaturated or partly saturated and has 5 or 6 ring members, 
     the ring B&#39; has no further substituents and n is defined above, and A n ⊖ signifies an anion, preferably a non-chromophoric anion. 
     The invention also provides a process for the production of a compound of formula I, which comprise: 
     (a) coupling the diazo compound from an amine of formula XIV, 
     
         R.sub.1 --NH.sub.2                                         XIV 
    
     in which 
     R 1  is as defined above, with a coupling component of formula XV, ##STR12## in which B, n, R 2 , R 3 , R 4 , K and A are as defined above, 
     (b) quaternating a compound of formula XVI, ##STR13## in which R 1 , R 2 , R 3 , R 4  and B are as defined above, and 
     W signifies a group of the formula ##STR14## in which R 10 , R 11 , R 13  and Z are as defined above, to produce a compound of formula Ib, ##STR15## in which R 1  to R 4 , B, n and A are as defined above, and 
     K&#34; signifies a radical of formula IV, IVa, VI or VII as defined above, 
     (c) reacting an azo compound of formula XX, ##STR16## in which R 1  to R 4 , and B are as defined above, and 
     A&#39; signifies a radical which may be converted into an anion, 
     with a compound of formula XXI, XXII, XXIIa or XXIII, ##STR17## in which R 6  to R 12  are as defined above, to produce a compound of formula Ic, ##STR18## in which R 1  to R 4 , B, n and A&#39; are as defined above, and 
     K&#39;&#34; signifies a radical of formula III, IV, IVa or V as defined above, 
     (d) reacting a compound of formula XXIV, ##STR19## in which R 1  to R 4  and B are as defined above, and 
     W 1  signifies a group of formula LII as defined above or ##STR20## in which R 6  and R 7  are as defined above, with a compound of formula XXVI, 
     
         Ha1--NH.sub.2                                              XXVI 
    
     in which Ha1 signifies a halogen atom or a compound of formula XXVII, ##STR21## in which R 8  and R 9  are as defined above, to produce a compound of formula Id, ##STR22## in which R 1  to R 4 , B, n and A are as defined above, and 
     K iv  signifies a group of formula III as defined above or ##STR23## in which Z and R 13  are as defined above. 
     It will be appreciated that the anion A n ⊖ may be exchanged for another anion, for example with the aid of an ion exchanger or by reaction with salts or acids, if necessary in more than one step, for example via the hydroxide or bicarbonate. 
     The coupling reaction of a diazotized compound of formula XIV with a compound of formula XV may be carried out in conventional manner, e.g. in a neutral to acid medium at temperatures around 0° C., if necessary in the presence of a buffering agent. 
     The quaternation reaction of process variant (b) may be carried out in conventional manner, e.g. in an inert solvent or in aqueous suspension or without solvent in an excess of the quaternating agent, if necessary at high temperatures and in buffered medium. It is advantageous to use organic acids, if necessary in conjunction with a basic compound. 
     The suitable quaternating agents include alkyl halides, e.g. methyl and ethyl chloride, bromide and iodide, alkyl sulphates such as dimethyl sulphate, benzyl chloride, acrylic acid amides with hydrohalic acids e.g. CH 2  ═CH--CO--NH 2  /HCl, chloroacetic acid alkyl ester and β-chloropropionic amide, epoxides, e.g. ethylene oxide, propylene oxide and epichlorohydrin. Examples of quaternating agents are R 12  --A, R 14  --A and R 15  --A. 
     In process variant (c), the reaction of the compound of formula XX with a compound of formula XXI, XXII or XXIII is suitably carried out in an organic solvent in the temperature range of about -50° C. to +250° C., preferably at 10° C. to +120° C. This reaction can also be effected in aqueous medium, with or without the addition of an organic solvent, or in the absence of solvent, at the stated temperatures. 
     In process variant (d) the reaction of a compound of formula XVIII with a halogen amine of formula XXVI is suitably carried out in an organic solvent at temperatures from -50° C. to +80° C. The reaction can also be carried out in aqueous medium, if necessary with the addition of an organic solvent, at the stated temperatures, with the halogen amine added either in the form of the gas or in an organic solvent, in water or in a mixture of organic solvent and water. The use of chloroamine is preferred. 
     The reaction of a compound of formula XXIV is carried out in conventional manner with a compound of formula XXVII and is suitably carried out at -10° C. to +100° C. 
     The starting materials of these processes are known or can be produced from known compounds by known methods or analogously to known methods. 
     The compounds of formula I possess properties which indicate their usefulness in dyeing and printing fibres, yarns and textiles which consist of, or contain as component, fibres spun from homopolymers or copolymers of acrylonitrile or asymmetrical dicyanoethylene. The compounds are also indicated for use with synthetic polyamide and polyester fibres modified by the introduction of acid groups. Polyamide fibres of this type are described, for example, in Belgian Pat. No. 706,104. Analogous polyester fibres are described in U.S. Pat. No. 3,379,723. The compounds are also indicated for use in the dyeing of leather and paper and for the mass colouration of plastics. 
     The compounds are particularly indicated for use in exhaust dyeing in which they are applied from an aqueous neutral or acid medium, at 60° C. to the boil, or at temperatures above 100° C. under static pressure. 
     The compounds give level dyeings showing good fastness to light and wet treatment, and fastness to water, sea, water, washing, perspiration, sublimation, pleating, decatizing, pressing, steaming, dry cleaning, cross dyeing and common solvents is indicated. 
     The compounds are well soluble, especially in water, show good salt compatibility (e.g. with sulphates and thiocyanates) and pH stability, and are stable to boiling. They build up rapidly on the aforenamed substrates and reserve substrates for which they have no affinity, for example unmodified natural and synthetic polyamide fibres. 
     The compounds of this invention which are well soluble in organic solvents are indicated for use in the mass colouration of natural and synthetic polymers and natural and synthetic resins in the dissolved or undissolved state, for example, to dye tannin-treated cotton and regenerated cellulosic fibres. Furthermore, the compounds of the invention are suitable for dyeing using the Neochrome process. 
     It has been found that mixtures of two or more of the compounds or mixtures of isomers or mixtures of these with other dyes of cationic character can be employed with advantage under certain conditions. 
    
    
     In the following Examples the parts and percentages are by weight and the temperatures in degrees centigrade. 
     EXAMPLE 1 ##STR24## 
     (a) A nitrosylsulphuric acid solution is prepared with 27.2 parts of 96-98% sulphuric acid and 7.8 parts of 100% sodium nitrite. It is diluted with 40 parts of glacial acetic acid and 67 parts of 85% phosphoric acid and set for reaction with 9.2 parts (0.05 mols) of 5-amino-3-phenyl-1,2,4-thiadiazole, added gradually in portions. The solution is reacted for 9 hours at 0°-5° with stirring. After being clarified by filtration, the ice-cold, pale yellow diazo solution is dropped at 0°-5° into a solution of 20 parts of 63% 1-(1&#39;-methyl-2&#39;-N-methyl-N-phenylamino)-ethyl-1,1-dimethylhydrazinium chloride and 3 parts of aminosulphonic acid in 100 parts of water. At the same time 115 parts of ice are added. At 5° 38 parts of 30% sodium hydroxide solution and 100 parts of ice are entered into the clear solution, then 60  parts of sodium chloride are added to salt out the product. Stirring is continued for 4 hours, the product is then filtered and washed with 40 parts of a 20% solution of common salt in sulphuric acid. The filtercake is stirred into 300 parts of water at 40°, the pH adjusted to 5.5-6.0 with 3 parts of 30% sodium hydroxide solution and the suspension stirred for 2 hours. The product is filtered, washed again with 150 parts of 3% common salt solution and dried. 20.1 Parts of the product in 94.7% purity are obtained. 
     (b) The same product can be produced as follows. 37.2 parts of 3-phenyl-1,2,4-thiadiazole-(5 azo 4)-[1-(N-methyl-N-2&#39;-methyl-2&#39;-methyl-2&#39;-chloroethyl)-aniline] are dissolved in 300 parts of chlorobenzene and 4.5 parts of n-butanol at 50°-70°. In 30 minutes 6.6 parts of 1,1-dimethylhydrazine are added with stirring at 60°-80° under a nitrogen atmosphere. The solution is stirred for 1 hour and then cooled to 5°-10°, on which the product settles out in crystalline form. It is isolated by filtration and dried to give 27.6 parts of the product in 94.2% purity. 
     (c) The same product can be produced as follows. 38 Parts of 3-phenyl-1,2,4-thiadiazole-(5 azo 4)-1-(N-methyl-N-2&#39;-methyl-2&#39;-dimethylaminoethyl)-aniline are dissolved in 900 parts of chlorobenzene. In one hour 7.1 parts of freshly prepared gaseous chloramine are directed into the solution with vigorous stirring. The product settles out in the form of the salt and is filtered, washed with 50 parts of chlorobenzene and dried. It is obtained in a yield of 37.6 parts and in 93.8% purity. 
     (d) If hydroxylamine-0-sulphonic acid is used in place of chloramine, the procedure is as follows. 29 Parts of 1-(N-methyl-N-2&#39;-methyl-2&#39;-dimethylaminoethyl)-aniline are dissolved in 55 parts of water with 5 parts of glacial acetic acid. The solution is dropped at 95° into an ice-cold solution of 6 parts of hydroxylamine-0-sulphonic acid in 30 parts of water with vigorous stirring. The temperature is held at 95° for 20 minutes, then the solution is allowed to cool to 5°-10° and adjusted to pH 10 with sodium hydroxide solution. The unreacted starting product is extracted twice using 60 parts of benzene each time. The aqueous solution is weakly acidified with hydrochloric acid and the diazonium solution of 5-amino-3-phenyl-1,2,4-thiadiazole, prepared as in (a) above is added dropwise. The product is isolated as in (a) above. This procedure results in 18.2 parts of the dye in 93.6% purity. 
     EXAMPLE 2 ##STR25## 
     The diazo compound from 5-amino-3-phenyl-1,2,4-thiadiazole formed as in Example 1 is coupled with 10.5 parts of the compound of the formula ##STR26## in the presence of 3 parts of aminosulphonic acid and 80 parts of glacial acetic acid, with the simultaneous addition of 20 parts of ice. The product is worked up as described in Example 1, except that the solution is adjusted to pH 9-10 instead of 5.5-6.0. On drying, 17.2 parts of the product in 95.8% purity are obtained. 9.5 Parts of the powder product are dissolved in 250 parts of chlorobenzene. The solution is brought to the boil in 15 minutes with stirring, 6.3 parts of dimethyl sulphate are added and the solution held at the boil for a further 2 hours. It is evaporated to dryness in vacuum, the residue dissolved in 250 parts of water, and 25 parts of sodium chloride added to precipitate the product, which is isolated by filtration and dried. The dye is obtained in a yield of 19.1 parts in 92.3% purity. On polyacrylonitrile fibres and polyamide fibres modified by the introduction of acid groups it gives fast dyeings of red shade. 
     Example of Application 
     A mixture of 20 parts of the dye produced as in Example 1 and 80 parts of dextrin is ground for 48 hours in a ball mill to give a fine powder. One of the part of the powder is pasted with 1 part of 40% acetic acid and 200 parts of demineralized water are poured over the paste with stirring and boiling to dissolve. The solution is added to 7000 parts of demineralized water, to which 2 parts of glacial acetic are added. 100 parts of a fabric of polyacrylonitrile fibre, which may be previously treated for 10 to 15 minutes at 60° in a bath of 8000 parts of water and 2 parts of glacial acetic acid, are entered into a dyebath at 60°. The dyebath is raised to 98°-100° in 30 minutes and the fabric dyed at at this temperature for 11/2 hours. On removal it is rinsed and dried. A red dyeing of good light and wet fastness is obtained. 
     Table 1 gives the structural composition of further compounds which can be produced in analogy with the procedures of Example 1 or 2. They are of general formula Ie, ##STR27## where R 2  to R 4 , R 17  and K.sup.⊕ have the meanings noted in the pertinent columns. The anion A n ⊖ may be any one of those named in the foregoing. The symbol K 1-34 .sup.⊕ has the meanings given in Table A. 
     
                       Table A                                                     
______________________________________                                    
K.sup.⊕  in formulae Ie to Ih may represent                           
any one of the radicals                                                   
K.sub.1.sup.⊕  to K.sub.34.sup.⊕  , which signify:                
______________________________________                                    
K.sub.1       N(CH.sub.3).sub.3 ] .sup.⊕                              
K.sub.2       N(C.sub.2 H.sub.5).sub.3 ] .sup.⊕                       
K.sub.3                                                                   
               ##STR28##                                                  
K.sub.4                                                                   
               ##STR29##                                                  
K.sub.5       N(C.sub.2 H.sub.4 OH).sub.3 ].sup.⊕                     
K.sub.6                                                                   
               ##STR30##                                                  
K.sub.7                                                                   
               ##STR31##                                                  
K.sub.8                                                                   
               ##STR32##                                                  
K.sub.9                                                                   
               ##STR33##                                                  
K.sub.10                                                                  
               ##STR34##                                                  
K.sub.11                                                                  
               ##STR35##                                                  
K.sub.12                                                                  
               ##STR36##                                                  
K.sub.13                                                                  
               ##STR37##                                                  
K.sub.14                                                                  
               ##STR38##                                                  
K.sub.15                                                                  
               ##STR39##                                                  
K.sub.16                                                                  
               ##STR40##                                                  
K.sub.17                                                                  
               ##STR41##                                                  
K.sub.18                                                                  
               ##STR42##                                                  
K.sub.19                                                                  
               ##STR43##                                                  
K.sub.20                                                                  
               ##STR44##                                                  
K.sub.21                                                                  
               ##STR45##                                                  
K.sub.22                                                                  
               ##STR46##                                                  
K.sub.23                                                                  
               ##STR47##                                                  
K.sub.24                                                                  
               ##STR48##                                                  
K.sub.25                                                                  
               ##STR49##                                                  
K.sub.26                                                                  
               ##STR50##                                                  
K.sub.27                                                                  
               ##STR51##                                                  
K.sub.28                                                                  
               ##STR52##                                                  
K.sub.29                                                                  
               ##STR53##                                                  
K.sub.30                                                                  
               ##STR54##                                                  
K.sub.31                                                                  
               ##STR55##                                                  
K.sub.32                                                                  
               ##STR56##                                                  
K.sub.33                                                                  
               ##STR57##                                                  
K.sub.34                                                                  
               ##STR58##                                                  
______________________________________                                    
 
    
     
                                           Table I                                 
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                                   Shade of dyeing on                     
No.                                                                       
   R.sub.2   R.sub.3                                                      
                 R.sub.4   R.sub.17                                       
                                K.sup.⊕                               
                                   polyacrylonitrile fibre                
__________________________________________________________________________
3  CH.sub.3  H   CH.sub.3  H    K.sub.2                                   
                                   red                                    
4  &#34;         H   &#34;         H    K.sub.3                                   
                                   &#34;                                      
5  &#34;         H   &#34;         H    K.sub.4                                   
                                   &#34;                                      
6  &#34;         H   &#34;         H    K.sub.5                                   
                                   &#34;                                      
7  &#34;         H   &#34;         H    K.sub.6                                   
                                   &#34;                                      
8  &#34;         H   &#34;         H    K.sub.7                                   
                                   &#34;                                      
9  &#34;         H   &#34;         H    K.sub.8                                   
                                   &#34;                                      
10 &#34;         H   &#34;         H    K.sub.9                                   
                                   &#34;                                      
11 &#34;         H   &#34;         H    K.sub.10                                  
                                   &#34;                                      
12 &#34;         H   &#34;         H    K.sub.11                                  
                                   &#34;                                      
13 &#34;         H   &#34;         H    K.sub.12                                  
                                   &#34;                                      
14 &#34;         H   &#34;         H    K.sub.13                                  
                                   &#34;                                      
15 &#34;         H   &#34;         H    K.sub.14                                  
                                   &#34;                                      
16 &#34;         H   &#34;         H    K.sub.15                                  
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17 &#34;         H   &#34;         H    K.sub.16                                  
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18 &#34;         H   &#34;         H    K.sub.17                                  
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19 &#34;         H   &#34;         H    K.sub.18                                  
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20 &#34;         H   &#34;         H    K.sub.20                                  
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21 &#34;         H   &#34;         H    K.sub.21                                  
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22 &#34;         H   &#34;         H    K.sub.22                                  
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23 &#34;         H   &#34;         H    K.sub.23                                  
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24 &#34;         H   &#34;         H    K.sub.24                                  
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25 &#34;         H   &#34;         H    K.sub.25                                  
                                   &#34;                                      
26 &#34;         H   &#34;         H    K.sub.26                                  
                                   &#34;                                      
27 &#34;         H   &#34;         H    K.sub.27                                  
                                   &#34;                                      
28 &#34;         H   &#34;         H    K.sub.28                                  
                                   &#34;                                      
29 &#34;         H   &#34;         H    K.sub.29                                  
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30 &#34;         H   &#34;         H    K.sub.30                                  
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31 &#34;         H   &#34;         H    K.sub.31                                  
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32 &#34;         H   &#34;         H    K.sub.32                                  
                                   &#34;                                      
33 &#34;         H   &#34;         H    K.sub.33                                  
                                   &#34;                                      
34 &#34;         H   &#34;         H    K.sub.34                                  
                                   &#34;                                      
35 &#34;         CH.sub.3                                                     
                 H         H    K.sub.1                                   
                                   &#34;                                      
36 &#34;         &#34;   H         H    K.sub.2                                   
                                   &#34;                                      
37 &#34;         &#34;   H         H    K.sub.3                                   
                                   &#34;                                      
38 &#34;         &#34;   H         H    K.sub.4                                   
                                   &#34;                                      
39 &#34;         &#34;   H         H    K.sub.5                                   
                                   &#34;                                      
40 &#34;         &#34;   H         H    K.sub.6                                   
                                   &#34;                                      
41 &#34;         &#34;   H         H    K.sub.7                                   
                                   &#34;                                      
42 &#34;         &#34;   H         H    K.sub.8                                   
                                   &#34;                                      
43 &#34;         &#34;   H         H    K.sub.9                                   
                                   &#34;                                      
44 &#34;         &#34;   H         H    K.sub.10                                  
                                   &#34;                                      
45 &#34;         &#34;   H         H    K.sub.11                                  
                                   &#34;                                      
46 &#34;         &#34;   H         H    K.sub.12                                  
                                   &#34;                                      
47 &#34;         &#34;   H         H    K.sub.13                                  
                                   &#34;                                      
48 &#34;         &#34;   H         H    K.sub.14                                  
                                   &#34;                                      
49 &#34;         &#34;   H         H    K.sub.15                                  
                                   &#34;                                      
50 &#34;         &#34;   H         H    K.sub.17                                  
                                   &#34;                                      
51 &#34;         &#34;   H         H    K.sub.19                                  
                                   &#34;                                      
52 &#34;         &#34;   H         H    K.sub.20                                  
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53 &#34;         &#34;   H         H    K.sub.21                                  
                                   &#34;                                      
54 &#34;         &#34;   H         H    K.sub.23                                  
                                   &#34;                                      
55 &#34;         &#34;   H         H    K.sub.24                                  
                                   &#34;                                      
56 &#34;         &#34;   H         H    K.sub.28                                  
                                   &#34;                                      
57 &#34;         &#34;   H         H    K.sub.29                                  
                                   &#34;                                      
58 &#34;         &#34;   H         H    K.sub.30                                  
                                   &#34;                                      
59 &#34;         &#34;   H         H    K.sub.31                                  
                                   &#34;                                      
60 &#34;         &#34;   H         H    K.sub.33                                  
                                   &#34;                                      
61 &#34;         &#34;   H         H    K.sub.34                                  
                                   &#34;                                      
62 C.sub.2 H.sub.5                                                        
             H   CH.sub.3  H    K.sub.1                                   
                                   &#34;                                      
63 &#34;         H   &#34;         H    K.sub.3                                   
                                   &#34;                                      
64 &#34;         H   &#34;         H    K.sub.19                                  
                                   &#34;                                      
65 &#34;         H   &#34;         H    K.sub.33                                  
                                   &#34;                                      
66 &#34;         H   &#34;         H    K.sub.34                                  
                                   &#34;                                      
67 &#34;         H   &#34;         H    K.sub.10                                  
                                   &#34;                                      
68 &#34;         CH.sub.3                                                     
                 H         H    K.sub.1                                   
                                   &#34;                                      
69 &#34;         &#34;   H         H    K.sub.3                                   
                                   &#34;                                      
70 &#34;         &#34;   H         H    K.sub.10                                  
                                   &#34;                                      
71 &#34;         &#34;   H         H    K.sub.19                                  
                                   &#34;                                      
72 &#34;         &#34;   H         H    K.sub.33                                  
                                   &#34;                                      
73 &#34;         &#34;   H         H    K.sub.34                                  
                                   &#34;                                      
74 C.sub.4 H.sub.9                                                        
             H   CH.sub.3  H    K.sub.1                                   
                                   &#34;                                      
75 &#34;         H   &#34;         H    K.sub.3                                   
                                   &#34;                                      
76 &#34;         H   &#34;         H    K.sub.10                                  
                                   &#34;                                      
77 &#34;         H   &#34;         H    K.sub.19                                  
                                   &#34;                                      
78 C.sub.2 H.sub.4 CN                                                     
             H   &#34;         H    K.sub.1                                   
                                   &#34;                                      
79 &#34;         H   &#34;         H    K.sub.10                                  
                                   &#34;                                      
80 &#34;         H   &#34;         H    K.sub.19                                  
                                   &#34;                                      
81                                                                        
    ##STR59##                                                             
             H   &#34;         H    K.sub.1                                   
                                   &#34;                                      
82 &#34;         H   &#34;         H    K.sub.10                                  
                                   &#34;                                      
83 &#34;         H   &#34;         H    K.sub.19                                  
                                   &#34;                                      
84 C.sub.2 H.sub.4 COOC.sub.2 H.sub.5                                     
             H   &#34;         H    K.sub.1                                   
                                   &#34;                                      
85 &#34;         H   &#34;         H    K.sub.10                                  
                                   &#34;                                      
86 &#34;         H   &#34;         H    K.sub.19                                  
                                   &#34;                                      
87 CH.sub.3  CH.sub.3                                                     
                 &#34;         H    K.sub.1                                   
                                   &#34;                                      
88 &#34;         &#34;   &#34;         H    K.sub.10                                  
                                   &#34;                                      
89 &#34;         &#34;   &#34;         H    K.sub.19                                  
                                   &#34;                                      
90 &#34;         H                                                            
                  ##STR60##                                               
                           H    K.sub.1                                   
                                   &#34;                                      
91 &#34;         H   &#34;         H    K.sub.10                                  
                                   &#34;                                      
92 &#34;         H   &#34;         H    K.sub.19                                  
                                   &#34;                                      
93 C.sub.2 H.sub.5                                                        
             H   CH.sub.3  CH.sub.3                                       
                                K.sub.1                                   
                                   &#34;                                      
94 &#34;         H   &#34;         &#34;    K.sub.2                                   
                                   &#34;                                      
95 &#34;         H   &#34;         &#34;    K.sub.3                                   
                                   &#34;                                      
96 &#34;         H   &#34;         &#34;    K.sub.4                                   
                                   &#34;                                      
97 &#34;         H   &#34;         &#34;    K.sub.5                                   
                                   &#34;                                      
98 &#34;         H   &#34;         &#34;    K.sub.6                                   
                                   &#34;                                      
99 &#34;         H   &#34;         &#34;    K.sub.7                                   
                                   &#34;                                      
100                                                                       
   &#34;         H   &#34;         &#34;    K.sub.8                                   
                                   &#34;                                      
101                                                                       
   &#34;         H   &#34;         &#34;    K.sub.9                                   
                                   &#34;                                      
102                                                                       
   &#34;         H   &#34;         &#34;    K.sub.10                                  
                                   &#34;                                      
103                                                                       
   &#34;         H   &#34;         &#34;    K.sub.11                                  
                                   &#34;                                      
104                                                                       
   &#34;         H   &#34;         &#34;    K.sub.12                                  
                                   &#34;                                      
105                                                                       
   &#34;         H   &#34;         &#34;    K.sub.13                                  
                                   blue-red                               
106                                                                       
   &#34;         H   &#34;         &#34;    K.sub.14                                  
                                   &#34;                                      
107                                                                       
   &#34;         H   &#34;         &#34;    K.sub.15                                  
                                   &#34;                                      
108                                                                       
   &#34;         H   &#34;         &#34;    K.sub.16                                  
                                   &#34;                                      
109                                                                       
   &#34;         H   &#34;         &#34;    K.sub.17                                  
                                   &#34;                                      
110                                                                       
   &#34;         H   &#34;         &#34;    K.sub.18                                  
                                   &#34;                                      
111                                                                       
   &#34;         H   &#34;         &#34;    K.sub.19                                  
                                   &#34;                                      
112                                                                       
   &#34;         H   &#34;         &#34;    K.sub.20                                  
                                   &#34;                                      
113                                                                       
   &#34;         H   &#34;         &#34;    K.sub.21                                  
                                   &#34;                                      
114                                                                       
   &#34;         H   &#34;         &#34;    K.sub.22                                  
                                   &#34;                                      
115                                                                       
   &#34;         H   &#34;         &#34;    K.sub.23                                  
                                   &#34;                                      
116                                                                       
   &#34;         H   &#34;         &#34;    K.sub.24                                  
                                   &#34;                                      
117                                                                       
   &#34;         H   &#34;         &#34;    K.sub.25                                  
                                   &#34;                                      
118                                                                       
   &#34;         H   &#34;         &#34;    K.sub.26                                  
                                   &#34;                                      
119                                                                       
   &#34;         H   &#34;         &#34;    K.sub.27                                  
                                   &#34;                                      
120                                                                       
   &#34;         H   &#34;         &#34;    K.sub.28                                  
                                   &#34;                                      
121                                                                       
   &#34;         H   &#34;         &#34;    K.sub.29                                  
                                   &#34;                                      
122                                                                       
   &#34;         H   &#34;         &#34;    K.sub.30                                  
                                   &#34;                                      
123                                                                       
   &#34;         H   &#34;         &#34;    K.sub.31                                  
                                   &#34;                                      
124                                                                       
   &#34;         H   &#34;         &#34;    K.sub.32                                  
                                   &#34;                                      
125                                                                       
   &#34;         H   &#34;         &#34;    K.sub.33                                  
                                   &#34;                                      
126                                                                       
   &#34;         H   &#34;         &#34;    K.sub.34                                  
                                   &#34;                                      
127                                                                       
   &#34;         CH.sub.3                                                     
                 H         &#34;    K.sub.1                                   
                                   &#34;                                      
128                                                                       
   &#34;         &#34;   H         &#34;    K.sub.10                                  
                                   &#34;                                      
129                                                                       
   &#34;         &#34;   H         &#34;    K.sub.19                                  
                                   &#34;                                      
130                                                                       
    ##STR61##                                                             
             H   &#34;         &#34;    K.sub.1                                   
                                   &#34;                                      
131                                                                       
   &#34;         H   &#34;         &#34;    K.sub.10                                  
                                   red                                    
132                                                                       
   &#34;         H   &#34;         &#34;    K.sub.19                                  
                                   &#34;                                      
133                                                                       
   C.sub.2 H.sub.5                                                        
             CH.sub.3                                                     
                 &#34;         &#34;    K.sub.1                                   
                                   blue-red                               
134                                                                       
   &#34;         H   &#34;         OCH.sub.3                                      
                                K.sub.1                                   
                                   &#34;                                      
135                                                                       
   &#34;         H   &#34;         &#34;    K.sub.10                                  
                                   &#34;                                      
136                                                                       
   &#34;         H   &#34;         &#34;    K.sub.19                                  
                                   &#34;                                      
137                                                                       
   &#34;         H   &#34;         Cl   K.sub.1                                   
                                   &#34;                                      
138                                                                       
   &#34;         H   &#34;         &#34;    K.sub.19                                  
                                   &#34;                                      
__________________________________________________________________________
 
    
     Table II below shows the structural composition of further dyes which can be produced in accordance with the procedure of Example 1 or 2. They are of general formula If, ##STR62## where R 2  to R 4 , R 17 , K.sup.⊕ and R 18  have the meanings given in the table. The anion A.sup.⊖ may be any one of those named in the foregoing. 
     
                                           Table II                                
__________________________________________________________________________
                                 Shade of dyeing on                       
                                 polyacrylonitrile                        
No.                                                                       
   R.sub.18  R.sub.2                                                      
                  R.sub.3                                                 
                      R.sub.4                                             
                          R.sub.17                                        
                              K.sup.⊕                                 
                                 fibre                                    
__________________________________________________________________________
139                                                                       
    ##STR63##                                                             
             CH.sub.3                                                     
                  H   CH.sub.3                                            
                          H   K.sub.1                                     
                                 red                                      
140                                                                       
   &#34;         &#34;    H   &#34;   H   K.sub.10                                    
                                 &#34;                                        
141                                                                       
   &#34;         &#34;    H   &#34;   H   K.sub.19                                    
                                 &#34;                                        
142                                                                       
    ##STR64##                                                             
             C.sub.2 H.sub.5                                              
                  H   &#34;   CH.sub.3                                        
                              K.sub.1                                     
                                 rubine                                   
143                                                                       
   &#34;         &#34;    H   &#34;   &#34;   K.sub.10                                    
                                 &#34;                                        
144                                                                       
   &#34;         &#34;    H   &#34;   &#34;   K.sub.19                                    
                                 &#34;                                        
145                                                                       
    ##STR65##                                                             
             &#34;    H   &#34;   &#34;   K.sub.1                                     
                                 bluish red                               
146                                                                       
   &#34;         &#34;    H   &#34;   &#34;   K.sub.10                                    
                                 &#34;                                        
147                                                                       
   &#34;         &#34;    H   &#34;   &#34;   K.sub.19                                    
                                 &#34;                                        
148                                                                       
   Cl        CH.sub.3                                                     
                  H   &#34;   H   K.sub.1                                     
                                 red                                      
149                                                                       
   &#34;         &#34;    H   &#34;   H   K.sub.10                                    
                                 &#34;                                        
150                                                                       
   &#34;         &#34;    H   &#34;   H   K.sub.19                                    
                                 &#34;                                        
151                                                                       
   &#34;         &#34;    CH.sub.3                                                
                      H   H   K.sub.1                                     
                                 &#34;                                        
152                                                                       
   &#34;         &#34;    &#34;   H   H   K.sub.10                                    
                                 &#34;                                        
153                                                                       
   &#34;         &#34;    &#34;   H   H   K.sub.19                                    
                                 &#34;                                        
154                                                                       
   &#34;         C.sub.2 H.sub.5                                              
                  &#34;   CH.sub.3                                            
                          CH.sub.3                                        
                              K.sub.1                                     
                                 bluish red                               
155                                                                       
   &#34;         &#34;    &#34;   &#34;   &#34;   K.sub.10                                    
                                 &#34;                                        
156                                                                       
   &#34;         &#34;    H   &#34;   &#34;   K.sub.19                                    
                                 &#34;                                        
157                                                                       
   C.sub.2 H.sub.5S                                                       
             CH.sub.3                                                     
                  H   CH.sub.3                                            
                          H   K.sub.1                                     
                                 blue-red                                 
158                                                                       
   &#34;         &#34;    H   &#34;   H   K.sub.10                                    
                                 &#34;                                        
159                                                                       
   &#34;         &#34;    H   &#34;   H   K.sub.19                                    
                                 &#34;                                        
160                                                                       
   C.sub.2 H.sub.5 SO.sub.2                                               
             &#34;    H   &#34;   H   K.sub.1                                     
                                 red                                      
161                                                                       
   &#34;         &#34;    H   &#34;   H   K.sub.10                                    
                                 &#34;                                        
162                                                                       
   &#34;         &#34;    H   &#34;   H   K.sub.19                                    
                                 &#34;                                        
163                                                                       
   &#34;         C.sub.2 H.sub.5                                              
                  H   &#34;   CH.sub.3                                        
                              K.sub.1                                     
                                 bluish red                               
164                                                                       
   &#34;         &#34;    H   &#34;   &#34;   K.sub.10                                    
                                 &#34;                                        
165                                                                       
   &#34;         &#34;    H   &#34;   &#34;   K.sub.19                                    
                                 &#34;                                        
166                                                                       
   CH.sub.3  CH.sub.3                                                     
                  H   CH.sub.3                                            
                          H   K.sub.1                                     
                                 red                                      
167                                                                       
   &#34;         &#34;    H   &#34;   H   K.sub.10                                    
                                 &#34;                                        
168                                                                       
   &#34;         &#34;    H   &#34;   H   K.sub.19                                    
                                 &#34;                                        
169                                                                       
   &#34;         C.sub.2 H.sub.5                                              
                  H   &#34;   CH.sub.3                                        
                              K.sub.1                                     
                                 bluish red                               
170                                                                       
   &#34;         &#34;    H   &#34;   &#34;   K.sub.10                                    
                                 &#34;                                        
171                                                                       
   &#34;         &#34;    H   &#34;   &#34;   K.sub.19                                    
                                 &#34;                                        
__________________________________________________________________________
 
    
     EXAMPLE 172 ##STR66## 
     EXAMPLE 173 ##STR67## 
     In Table III below the structural composition of further compounds is shown, which can be produced in accordance with the procedure of Example 1 or 2. They are of general formula Ig, ##STR68## where R 2  to R 4 , R 19  and K.sup.⊕ have the meanings given in the table. The anion A.sup.⊖ may be any one of those named in the foregoing. 
     
                                           Table III                               
__________________________________________________________________________
                                Shade of                                  
                                dyeing on                                 
                                polyacrylonitrile                         
No.                                                                       
  R.sub.19  R.sub.2                                                       
                 R.sub.3                                                  
                   R.sub.4                                                
                        R.sub.17                                          
                             K.sup.⊕                                  
                                fibre                                     
__________________________________________________________________________
174                                                                       
   ##STR69##                                                              
            CH.sub.3                                                      
                 H CH.sub.3                                               
                        H    K.sub.1                                      
                                scarlet                                   
175                                                                       
  &#34;         &#34;    H &#34;    H    K.sub.10                                     
                                &#34;                                         
176                                                                       
  &#34;         &#34;    H &#34;    H    K.sub.19                                     
                                &#34;                                         
177                                                                       
   ##STR70##                                                              
            C.sub.2 H.sub.5                                               
                 H &#34;    CH.sub.3                                          
                             K.sub.1                                      
                                red                                       
178                                                                       
  &#34;         &#34;    H &#34;    &#34;    K.sub.10                                     
                                &#34;                                         
179                                                                       
  &#34;         &#34;    H &#34;    &#34;    K.sub.19                                     
                                &#34;                                         
180                                                                       
   ##STR71##                                                              
            CH.sub.3                                                      
                 H &#34;    H    K.sub.1                                      
                                scarlet                                   
181                                                                       
  &#34;         &#34;    H &#34;    H    K.sub.10                                     
                                &#34;                                         
182                                                                       
  &#34;         &#34;    H &#34;    H    K.sub.19                                     
                                &#34;                                         
183                                                                       
   ##STR72##                                                              
            &#34;    H &#34;    H    K.sub.1                                      
                                &#34;                                         
184                                                                       
  &#34;         &#34;    H &#34;    H    K.sub.10                                     
                                &#34;                                         
185                                                                       
  &#34;         &#34;    H &#34;    H    K.sub.19                                     
                                &#34;                                         
186                                                                       
   ##STR73##                                                              
            C.sub.2 H.sub.5                                               
                 H &#34;    CH.sub.3                                          
                             K.sub.1                                      
                                red                                       
187                                                                       
  &#34;         &#34;    H &#34;    &#34;    K.sub.10                                     
                                &#34;                                         
188                                                                       
  &#34;         &#34;    H &#34;    &#34;    K.sub.19                                     
                                &#34;                                         
189                                                                       
   ##STR74##                                                              
            CH.sub.3                                                      
                 H &#34;    &#34;    K.sub.1                                      
                                scarlet                                   
190                                                                       
  &#34;         &#34;    H &#34;    &#34;    K.sub.10                                     
                                &#34;                                         
191                                                                       
  &#34;         &#34;    H &#34;    &#34;    K.sub.19                                     
                                &#34;                                         
__________________________________________________________________________
 
    
     EXAMPLE 192 ##STR75## 
     EXAMPLE 193 ##STR76## 
     EXAMPLE 194 ##STR77## 
     EXAMPLE 195 ##STR78## 
     In Table IV below gives the structural composition of further compounds which can be produced in accordance with the procedure of Example 1 or 2. They are of the formula ##STR79## where R 2  to R 4 , R 17 , R 20  and K.sup.⊕ have the meanings given in the table. The anion A.sup.⊖ may be any one of those named in the foregoing. 
     
                       Table IV                                                    
______________________________________                                    
                                          Shade of                        
                                          dyeing                          
                                          polyacrylo-                     
                                          nitrile                         
No.  R.sub.20                                                             
             R.sub.2 R.sub.3                                              
                         R.sub.4                                          
                               R.sub.17                                   
                                     K.sup.⊕                          
                                          fibre                           
______________________________________                                    
196  O.sub.2 N--                                                          
             --CH.sub.3                                                   
                     H   --CH.sub.3                                       
                               H     K.sub.1                              
                                          violet                          
197  &#34;       &#34;       H   &#34;     H     K.sub.10                             
                                          violet                          
198  &#34;       &#34;       H   &#34;     H     K.sub.19                             
                                          violet                          
199  &#34;       --C.sub.2 H.sub.5                                            
                     H   &#34;     --CH.sub.3                                 
                                     K.sub.1                              
                                          reddish blue                    
200  &#34;       &#34;       H   &#34;     &#34;     K.sub.10                             
                                          reddish blue                    
201  &#34;       &#34;       H   &#34;     &#34;     K.sub.19                             
                                          reddish blue                    
202  --CN    --CH.sub.3                                                   
                     H   &#34;     H     K.sub.1                              
                                          rubine                          
203  &#34;       &#34;       H   &#34;     H     K.sub.10                             
                                          rubine                          
204  &#34;       &#34;       H   &#34;     H     K.sub.19                             
                                          rubine                          
205  &#34;       --C.sub.2 H.sub.5                                            
                     H   &#34;     --CH.sub.3                                 
                                     K.sub.1                              
                                          violet                          
206  &#34;       &#34;       H   &#34;     &#34;     K.sub.10                             
                                          violet                          
207  &#34;       &#34;       H   &#34;     &#34;     K.sub.19                             
                                          violet                          
______________________________________                                    
 
    
     EXAMPLE 208 ##STR80## 
     EXAMPLE 209 ##STR81## 
     EXAMPLE 210 ##STR82## 
     EXAMPLE 211 ##STR83##