BE571743A - - Google Patents

Description

       

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   The present invention relates to new azo dyes and more especially to new water insoluble azo dyes useful for coloring textiles.



   It has been found that certain newer water insoluble azo dyes containing sulfonamide groups in which one or both hydrogen atoms have been replaced by chloroalkyl or bromoalkyl groups are superior, particularly when applied to polyamide-based textile materials with azo dyes already known in that they have good fixing properties and give colorations of exceptionally high strength to wet treatments.

   The colorations obtained on textile materials such as polyamide-based textiles with the aid of disperse dyes are generally deficient in fastness to wet treatments, but the colorations obtained with the new azo disperse dyes of the present invention on textile materials comprising fibers such as wool, silk, regenerated protein fibers, polyamide fibers or basic modified polyacrylonitrile fibers have excellent resistance to wet treatments not only because they retain the intensity of the shade but also because they bleed very little on neighboring textile materials. It seems that this fastness is due at least in part to a chemical reaction between the dye and the textile material.



   The invention provides novel water-insoluble azo dyes free from sulfonic acid, carboxylic acid and acylsulfonamido groups, which do not contain more than one enolizable phenolic, hydroxyl or carbonyl group and which contain at least one enolizable group. of the formula -SO2NRR 'each of which is directly attached to a different a.rylic ring in the azo dye, R representing a haloalkyl or halo-cycloalkyl radical, R' a hydrogen atom or a substituted or unsubstituted hydrocarbon radical or a radical haloalkyl or halo-cycloalkyl or alternatively R and R 'being joined to form with the nitrogen atom a heterocyclic ring containing a halogen atom.



   As examples of haloalkyl or halogenocycloalkyl radicals represented by R, mention may be made of the p-chloro-ethyl, ss-bromoethyl, p-chloropropyl, p-bromopropyle, # -chloro-ss-hydroxyproplye, y-bromo-hydroxypropy- radicals. the ;

     ss: @ - dichloropropyl, p-y-dibromopropyl, 2-chlorocyclohexyl, # -chloroprop-ss-yl and a-chlorobut-p-yl. As examples of the radicals represented by R ', mention may be made of the p-chlorethyl, p-bromethyl, p-chloropropyl, ss-bormopropyl, y-chloro-p-hydroxypropyle, # -bromo-ss-hydroxypropyle- radicals. 2-chlorocyclohexyl, methyl, ethyl, propyl, alkyl, cyclohexyl, benzyl, phenyl, ss-hydroxyethyl, P-ethoxyethyl, toluyl, chlorophenyl, methoxyphenyl and acetylaminophenyl.



   As examples of heterocyclic rings containing one or more chlorine or bromine atoms and formed from groups R, R 'and a nitrogen atom, mention may be made of the chloro and bromo derivatives of pyrrolidine, alkyl-pyrrolidines, and piperidine such as 3-chloropiperidine.



   The aryl ring present in the azo dye to which is attached an -SO, NRR 'group, defined above, may be a benzene or naphthalnic ring which may bear other substituents. As examples of these substituents, mention may be made of the alkyl groups, for example methyl, alkoxy, for example methoxy, halogen, for example chlorine or bromine, alkylsulfonyl, for example methylsulfonyl or ethylsufonyl, cyano, trifluoromethyl, dialkylamino for example dimethylamino or diethylamino, acylamino for example aoetylamino, and carbalkoxy for example carbomethoxy.



   According to another characteristic of the invention, in a process for preparing novel azo dyes which are insoluble in water, as defined above, an aromatic or heterocyclic amine is dinitrogenated and the diazo compound thus obtained is copulated with an element of coupling, the aromatic or heterocyclic amine and the coupling element being chosen so that the azo dye obtained is free from sulfonic, carboxylic and acylsulfonamido groups, does not con-

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 contains no more than one enolizable phenolic, hydroxyl or carbonyl group and contains at least one group of the formula -SO2NRR 'where R and R' are taken in the sense given above, each of the latter groups being attached to a different aryl nucleus present in the azo dye.



   The process of the invention can be advantageously carried out by adding sodium nitrite to a solution or a suspension of the aromatic or heterocyclic amine in an aqueous solution of an acid, for example hydrochloric acid, in adding the diazotized solution or suspension thus obtained to a solution of the coupling element in a suitable solvent such as water, adjusting the pH of the mixture to ensure that coupling occurs at a suitable rate and filtering the dye azo, insoluble in precipitating water.



  When the coupling takes place in the presence of a solvent, for example acetone, of the water insoluble azo dye, the dye is isolated preferably by adding water until all of the dye has been removed. precipitate.



   As examples of the aromatic and heterocyclic amines which can be used in the process of the invention, mention may be made of 2-, 3- or 4-.
 EMI2.1
 aminobenzenesulfon-N- (p-chloroethyl) amiàe, 2-, 3- or 4-aminobenzenesulfon-N- ((3 bromoethyl) amide, 2-amino-benzenesulfon-N- (y-chloropro-p-yl) amide, 2-chlc ro-4-aminobenzene-sulfon-N- (p-ohloroethyl) amide, 2: 5-dichloro-4-aminobenzene-sulfon-N- (p-chloroethyl) amide, 2-naphthylamine-6- sulfon-N- (p-chloroethyl) amide, 3- or ° -aminobenzenesulfon-N- (3-chloroethyl) methylamide 2-, 3- or 4-aminobenzene sulfon-N- (fi-chloroethyl) phenylamine, la 2-, 3- or 4-aminobenzenesulfon-N- (y-ohlo- ro-p-hydroxypropyl) phenylamide, 2-, 3- or ° -am.nobenzenesulfon-N- (2'-chloroç-clohexyl) amide, 2- , 3- or ° -aminobenzenesulfon-N- (3'-chloropiperidyl) amide la 2:

  5-d.methoxy- ° -aminoazobenzene - 3'-sulfon - N- (bta-vhloroethyl) amide aniline, ¯o- m- or p-toluidine, 2 ..-, m- or p-chloraniline, 2 ..-, z- or p-nitroaniline, 3-chlc ro-4-aminophenyl-methylsufone, 0-, ¯m- or p-anisidine, 5-nitro-2-aminothiazole, 6-ethoxy-2-aminobenzthiazole , 2-amino-5-nitrobenz'snesulfon N - ((3-chloroethyl, amide, 6-methylsulfonyl-2-aminobenzthiazole, -aminobenzotrifluoride,
 EMI2.2
 4-aminobenzonitrile, 2-carbomethoxyaniline, g-aminoacetanilide, 2: 5-di-methoxyaniline, alpha- or p-naphthylamine and 1-naphthylamine 4- or 5-sulfon-N- (p-chloroethyl) amide.



   The aromatic or heterocyclic amines used in the process of the invention and which contain a -SO2NRR 'group as defined above can be obtained from the corresponding amine which contains a sulfonic acid group by acetylating the amino group. , by converting the sulfonic acid to the corresponding sulfonyl chloride state, then by reacting with an amine of the formula -NHRR 'where R' and R 'are taken in the sense indicated above and finally by separating the group N-acetyl by hydrolysis.

   As a variant, amines can be obtained from the corresponding nitrosulfonic acids by transforming them into sulfonyl chloride, by reacting with an amine of the formula HNRR 'where R and R' are taken in the sense indicated above and then by re - reducing the nitro group to the state of amino group.



   As examples of coupling elements which can be used in the process of the invention, mention may be made of phenols, for example phenol,
 EMI2.3
 p-oreol and 27phenylphenol, naphthols, for example (3-naphthol and 2-naphthol-6-sulfon-N- (p-ohloroethyl) amide, arylamines, for example N-ethyl-Np-hydroxyethylaniline , 3-methyl N: N-di ((3-hydroxréthy) aniline 2-methoxy-5-methyl-N: N-di (p-hydroxyethyl) aniline, N-j3-hydroxy-ethyl-1-naphthylamine 2-naphthylamine-6-sulfon-N- (p-ohlproethyl) -amide, h-fi-cyanoethyl-1-naphthylamine, 3-methyl.

   N - ((3-hydroxy-ethyl) N - ((3-cyanoethyl) aniline9 3-N: N-diethylaminobenzenesulfon-N- (p-chloroethyl) amide, heterocyclic compounds containing enolizable CH2.C0 groups, for example 2g4-dihydroxyquinoline, 3-methyl-5-pyrazolone, 3-carbethoxy-5-pyrazolones 1 '- ((3-chloroethyl) aminosulfonyl phenyl-3-methyl-5-pyrazolone, and other compounds containing enolizable CH2.CO groups, for example acetoacetanilide and 3-acetoacetylaminobenzenesulfon-
 EMI2.4
 N- (p-chloroethyl) amide.

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   Phenols and naphthols which contain a -SO2NRR 'group, as defined above, can be obtained from the corresponding phenol or naphthol sulfonic acid by treating with p-toluenesulfonyl chloride, by reacting the op-toluenesulfonyl derivative thus obtained with phosphorus pentachloride, by treating the sulfonyl chloride thus obtained with an amine of the formula HNRR 'where R and R' are taken in the sense indicated above, then by separating by hydrolyzes the O-p-toluenesulfonyl group.



   Arylamines which contain a -SO2N44 'group, as defined above, can be obtained by converting the corresponding arylamine sulfonic acid to sulfonyl chloride and then treating with an amine of the formula HNRR' where R and R 'are taken in the sense indicated above.



   Pyrazolones which contain a -SO2NRR 'group as defined above can be obtained from the corresponding aromatic amine containing the -SO2NRR' group by diazotization, reduction to hydrazine, condensation with ethyl acetoacetate or acetoacetamide and closing the ring.



   Acetoacetarylides which contain a -SONRR 'group as defined above can be obtained from the corresponding aromatic amine containing the -SO2NRR' group by reacting the aromatic amine with a diketone.



   According to another feature of the invention, in another process for the preparation of new water-insoluble azo dyes, as defined above, the corresponding azo compound containing one or more sulfonic acid groups is converted to. sulfonyl chloride state, then treated with an amine of the formula HNRR 'where R and R' are taken in the sense indicated above.



   The azo compound containing one or more sulfonic acid groups used in this further process of the invention can be obtained by coupling a diazotized aromatic or heterocyclic primary amine with a coupling element, the aromatic or heterocyclic amine and the diazotized element. coupling being chosen so that the resulting azo compound is free from carboxylic acid or acylsulfonamide groups, does not contain more than one enolizable phenolic, hydroxyl or carbonyl group and contains at least one -SO3H group each of which is directly attached to a different aryl nucleus.



   If desired, the water insoluble azo dyes of the invention can be prepared in situ on the textile material by treating the textile material separately or simultaneously with an aqueous solution or dispersion of. a coupling member and by an aqueous solution or dispersion of an aromatic or heterocyclic amine in combination with a treatment with aqueous nitrous acid, the coupling member and the aromatic or heterocyclic amine being selected for that the resulting dye contains at least one group of the formula -SO2NRR 'as defined above, does not contain more than one enolizable phenolic, hydroxyl or carbonyl group and is free of sulfonic acid, carboxylic acid and acylsulfonamido.



   The novel water insoluble azo dyes as defined above can be used to color textile materials including animal fibers such as wool, silk and regenerated protein fibers, and artificial fibers such as ester fibers. cellulose, for example secondary cellulose acetate and cellulose triacetate, polyamide, polyurethane, polyester, polyacrylonitrile and modified polyacrylonitrile fibers, by treating the textile materials with aqueous dispersions of the dyes.

   The aqueous dispersions of the dyes can be obtained by methods known and described for the dispersion of dyes in general, for example by grinding with the aid of dispersing agents such as the sodium salt of sulfonated naphthalene condensation products and formaldehyde with or without the addition of protective colloids, for example dextrin. Dyes can, if de-

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 sire to be made into a dispersible powder. Substances known to facilitate: or improve dyeing, for example dispersing agents and protective colloids described above and electrolytes can be added to the dye bath.



   The dyes can be applied to textile materials at a temperature equivalent to or near the boiling point of the dye bath, preferably at a temperature between 75 and 100 C or if desired at a temperature. higher, for example a temperature between 100 and 130 0 under a pressure greater than atmospheric pressure. Textile materials which are not stable at temperatures above 90 C, for example secondary cellulose acetate, are preferably dyed at temperatures between 60 and 85 C.



   In the dyeing of textile materials based on cellulose triacetate or on polyester with the dyes of the invention, it is sometimes advantageous to use a blowing agent or another vehicle, for example diphenyl, dichlorobenzene or trichlorethylene.



   The new water insoluble dyes can also be applied to textile materials in the form of a thickened printing paste containing a fine dispersion of the dye. The printing paste can be thickened using customary thickening agents, for example methylcellulose, starch, locust bean gum, Nafka crystalline gum or sodium alginate, and may contain normal aids for printing pastes eg urea, thiourea or thiodiglycol, disperse dye application aids such as methyl alcohol, sodium meta-nitrobenzenesulfonate or aqueous emulsions of sulfonated oils, blowing agents or dyeing "vehicles" such as diphenyl.



   The printing paste can be advantageously applied to the textile material by board, spray, stencil, silk screen or roller, preferably by drying the printed materials and if desired by spraying. risking at a pressure greater than atmospheric pressure when a temperature greater than 100 ° C., preferably between 110 and 130 ° C. is required.



   If desired, the water insoluble azo dyes as defined above can be applied to man-made textile materials in combination with treatment with an amine, phenol or thiophenol, which can be applied to the textile material before simultaneously or after the application of the dye.



   Used on textile materials including wool, silk or regenerated protein fibers or man-made fibers such as polyamide fibers or basic modified polyacrylonitrile fibers, the new water insoluble azo dyes defined above, give remarkable colorings for their great fastness to wet treatments.



     A preferred class of the new azo insoluble azo dyes defined above are the azo dyes which contain a sulfon- group.
 EMI4.1
 N- (p-chloroethyl) amiàe or sulfon N - ((3-bromethyl) amide attached to an aryl ring present in coloran-b azo
As examples of this preferred class of water-insoluble azo dyes, as defined above, there may be mentioned the dyes of
 EMI4.2
 formula: X Y.C2H.HN02S / N - N - B - D where B represents the residue of a substituted or unsubstituted benzene or naphthalene ring, D represents a substituted or unsubstituted amino group, X a hydrogen atom or

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 of halogen and '? * an atom of chlorine, or of bromine.



   As examples of the substituents which may be present in the benzene or naphthalene ring represented by B, there may be mentioned the alkyl groups, such as methyl, trifluoromethyl, alkoxy such as methoxy, halogen such as chlorine and bromine and acidylamino such as acetylamino.



   As examples of substituted amino groups represented by B,
 EMI5.1
 may cite the methylamino, ethylamino, p-hyànoxyethylamino, (3-cyanoethyl-- amino, dimethylamino, diethylamino, di ((3-hydroxyethyl) amino methyl-fi-hydroxyethyl-amino, ethyl- (3-hydroxyalkylamino (3-cyanoethyl- ( 3-hydroxyethylaminoy-cyanoethyl-i-methoxyethylamino, ethyl- (3: yd.hydroxypropylamino and butyl- (3 hydoxyethylamino and as examples of the halogen atoms represented by X there may be mentioned chlorine and bromine.



   Applied to textiles, the dyes in this formula give orange to purple tones which are not phototropic and exhibit excellent fastness to light and wet treatments.



   As examples of the preferred class of water-insoluble azo dyes, defined above, there may be mentioned the dyes of the formula:
 EMI5.2
 
 EMI5.3
 or r represents an aryl or heuerocyclic nucleus SUOSu2uue or not, r represents a chlorine or bromine atom and Z and Z 'represent substituted or unsubstituted alkyl radicals and may be identical or different.



   As examples of substituted aryl or heterocyclic rings or
 EMI5.4
 not represented by T '-. one can quote the groups jg-nitrophenyl, 2-chloro-4-nitro-phenyl, -sulfonamidophenyle, 2-ohloro-4-ethylsulfonylphenyle, -cyano-2-triflu- oromi-thylphenyley 2-cyano -4-nitrophenyl, 4-nitro-2-trifluoromethylphenyl, 2-chlo-ro-4-P'-hydroxyethylsulfonylphenyl, 5-nitrothiazol-2-yl, 6-nitro-benzthiazol-2-yl and 6-methylsulfonylbenzothiazol-2- yle.



   As examples of alkyl radicals substituted or not represented by
 EMI5.5
 Z and Z 'include methyl, ethyl, butyl, P-hydroxyethyl, (3-oy-anoethyl and -meth4xyethyl) radicals.



   Applied to artificial textile materials comprising polyamide fibers, the dyes of this formula provide organo to blue shades possessing excellent fastness to wet treatments.



   As further examples of the preferred class of new water-insoluble azo dyes defined above, there may be mentioned the dyes of the formula:
 EMI5.6
 where Y represents a chlorine or bromine atom and the benzene rings may have substituents.



   As examples of these substituents there will be mentioned halogens such as chlorine and bromine, alkyl groups such as methyl and tert-butyl, alkoxy such as methoxy and aryl such as phenyl.

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   Applied to artificial textile materials, the dyes of this formula give yellow tones which are not phototropic and which have excellent fastness to wet treatments and to light.



   As further examples of the preferred class of new water insoluble azo dyes defined above, the dyes can be retained; of the formula:
 EMI6.1
 where Y represents a chlorine or bromine atom and where the benzene rings may have substituents.



   As examples of these substituents, there may be mentioned halogens such as chlorine or bromine, alkyl groups such as methyl, alkoxy such as methoxy,
 EMI6.2
 trifluoromethyl, sulfonamido or sulfonamido substituted as sufon- (3 hydroxyethyl) amido, and acidylamino as acetylamino, but it is preferable that the benzene nucleus is substituted with an alkyl group or a halogen atom in the 2 'position.



   Applied to artificial textile materials, the dyes in this formula give greenish-yellow tones with excellent fastness to wet treatments and to light.



   The invention is illustrated but not limited by the following examples where parts and proportions are by weight.



  EXAMPLE 1.-
A solution of 6.9 parts of sodium nitrite in 50 parts of water is gradually added to a solution of 27.1 parts of sodium hydrochloride.
 EMI6.3
 ° -aminobenzenesulfon-N- (j3-chloroethyl) amide in a mixture of 400 parts of water and 15 parts of a 36% aqueous solution of hydrochloric acid at a temperature between 15 and 20 C. The solution thus obtained is added over 20 minutes to a solution of 16.5 parts of N-ethyl-Np-hydroxyethylaniline in a mixture of 200 parts of water and 11.2 parts of a 36% aqueous solution of hydrochloric acid at a temperature of 0 to 5 C. After stirring the mixture for 2 hours, it is neutralized with Congo red by adding 55 parts of a 30% aqueous solution of sodium acetate over 30 minutes .

   After 5 minutes the
 EMI6.4
 Insoluble 4- (p-chloroethyl) aminosulfonyl-4'-N-ethyl-N- (p-hydroxyethyl) amino-benz is filtered off, washed with water and dried.



   1 part of the product thus obtained is dispersed in 20 parts of water by grinding in the presence of a sodium salt of a condensation product of sulfonated naphthalene and formaldehyde and the dispersion obtained is added to 4000 parts; of water containing 4 parts of a condensation product of ethylene oxide with a fatty alcohol. 100 parts of the polyamide-based textile material are placed in the resulting dyeing bath and the dyeing bath is then heated to 95 ° C. and maintained at this temperature for 60 minutes. The nylon fabric is then rinsed in water, immersed for 30 minutes in a hot aqueous solution containing 0.2% sodium carbonate and 0.1% of a condensation product of ethylene oxide with an alkylphenol, rinsed again with water and dried.

   The polyamide-based textile material is dyed an orange tone with very good wash fastness.



   If the textile material is replaced by 100 parts of secondary cellulose acetate and the dye bath is heated at 8500 for 60 minutes;

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 cellulose acetate is dyed orange.



    EXAMPLE 2. -. The 16.5 parts of N-ethyl-N-p-hydroxyethylaniline used are replaced.
 EMI7.1
 read in Example 1 by 1915 parts of N: N-di - ((3-hydroxyethyl) -¯m-toluidine.



  This gives 4- (p-chloroethyl) anosulfonyl-2'-methyl-4'-N: N-di (. (3-hydroxyethyl) aminoazobenzene which dyes secondary cellulose acetate in orange tones and textiles based on of polyamide in orange tones with very good fastness to light.



   The degree of fixation of the dye on the dyed nylon is determined as follows:
The dyed polyamide-based textile material is successively extracted with n-propanol at 85 ° C. until further treatments with n-propanol no longer remove the dye from the nylon. The amount of dye remaining in the textile material is then determined by dissolving the polyamide in o-chlorophenol and determining the dye colorimetrically. Comparison with the same amount of dye detected in an identical weight of similarly dyed polyamide-based textile material prior to n-propanol extraction gives a degree of fixation 69%. .



   In a similar test on a polyamide-based textile material
 EMI7.2
 dyed with 4 - (@ - hydroxyethyl) am] nosulfonyl-2'-methyl-4'-lT: N-di (fi-hyd # ôxyéthy $) aminobenzene all of the dye is extracted with n-propanol at 85 C .



   The following table contains other examples of prepared dyes
 EMI7.3
 by reacting diazotized 4-aminobenzenesulfon-N- (fi-chloroethyl) amide with arylamine-type coupling elements according to the process of Example 1.
 EMI7.4
 
<tb>



  Example <SEP> Element <SEP> of copulation <SEP> Tones <SEP> obtained <SEP> on
<tb> <SEP> textile <SEP> materials to
<tb>
 
 EMI7.5
 ¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ 3 N polyamide base: N-di- (2-hydroxyethyl ) amino-2-methoxy- reddish-yellow 5-methyl'benzene 4 N-2-hydroxyethyl-N-21-aminoethylaniline reddish-yellow 5 N-2-hydroxyethyl-N-2'-cyanoethyl-m-tolui- orange- yellowish
 EMI7.6
 
<tb> dine
<tb>
<tb> 6 <SEP> N-2-hydroxyethyl-alpha-naphthylamine <SEP> red
<tb>
<tb> 7 <SEP> N-p-hydroxyethyl-2-naphthylamine <SEP> bright red <SEP>
<tb>
 
 EMI7.7
 8 N: N-di (fi-hyroxyethyl) aniline orange 9 N- (3-hyd roxyethyl-N - cyanoethylaniline yellow-reddish 10 3-N: N-diethylaminobenzenesulion-N- orange ((3-chloroethylamide 11 2-naphthylamine -6-orange sulfonamide 12 2-naphthylamine-6-sulfon-N- (p-chloro-orange ethyl) amide 13 3-hydroxy-1: 2: 3: ° -tetrahdro-7:

  8- ruby l ': 2'-benzoquinoline 14 .2-N.-N-di (P-hydroxyeth3rl) amino-4- red acetylaminoanisole 15 1-Np-hydnoxyethylamino- (5: 8-dichlor- red naphthalene 16 1- Np-hydroxyethylamino-4-chloro-rose
 EMI7.8
 
<tb> naphthalene
<tb>
 

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 EMI8.1
 17 2-ethoxy-1-naphthylamine bluish-red 18 5: 6g7: 8-tetnahydro-i-N: N-di- (p-hydroxy- orange
 EMI8.2
 
<tb> ethyl) naphthylamine
<tb>
 
The attachment to the polyamide-based textile material reaches 74% in the case of Example 5 and 70% in the case of Example 6.



  EXAMPLE 19.-
30.55 parts of 4-chloro-3-aminobenzene- hydrochloride are dissolved. sulfon-Np-chloroethylamide by heating in a mixture of 200 parts of acetic acid and 15 parts of a 36% aqueous solution of hydrochloric acid and the solution is cooled to between 15 and 20 C. To the suspension thus obtained is added in 10 minutes a solution of 6.9 parts of sodium nitrite in 50 parts of water. Then 200 parts of water are added and the resulting suspension of the diazonium compound is added over 20 minutes to a solution of 19.5 parts.
 EMI8.3
 of N: N-di (3-hydroxyethyl-m toZuidine in a mixture of 180 parts of water and 18 parts of a 36% aqueous solution of hydrochloric acid at a temperature between 0 and 5 C.

   The mixture is stirred for 30 minutes, neutralized with Congo red by slowly adding 70 parts of a 30% aqueous acetate solution.
 EMI8.4
 sodium, then stirring for another 5 minutes. The 2-chloro-4- (P-chloroethyl ariinosulfonyl-21-methyl-41-N: N-di (P-hyd: roxyethyl) aminobenzene thus obtained is then separated by filtration, washed with water and dried. aqueous medium it dyes secondary cellulose acetate in orange-reddish tones and polyamide-based textiles in scarlet tones with very good wash fastness.



   The fixation of the dye on the dyed nylon is 69 EXAMPLE 20. -
A solution of 6.9 parts of sodium nitrite in 50 parts of water is gradually added to a 10 ° C solution of 27.1 parts of hydrochloride.
 EMI8.5
 te of 3-aminobenzensuifon-N- (p-chiono-ethyl) amide in a mixture of 480 parts of water and 15 parts of a 36% aqueous solution of hydrochloric acid. The solution thus obtained is added over the course of 10 minutes to a solution of 10.9 parts of -cresol and 10.8 parts of sodium carbonate in a mixture of 240 parts of water and 8 parts of sodium carbonate. 32% aqueous sodium hydroxide solution
 EMI8.6
 at 0 ° C. The 3- (fi-ohloroethyl) -aminosulfonyl-2'-hydroxy-5-methylazobenzene is separated by filtration, washed with water and dried.

   Dispersed in an aqueous medium, it dyes polyamide-based textiles in yellow tones with good wash fastness.



   The table below gives the shades obtained on the polyamide-based textile materials using dyes obtained by coupling in a similar manner.
 EMI8.7
 The diazotized 3-aminobenzenesulfon-N- (p-chloroethyl) amide can be linked with the coupling elements specified in the second column of the table.
 EMI8.8
 
<tb>



  Example <SEP> Element <SEP> of <SEP> copulation <SEP> Tones <SEP> obtained <SEP> on
<tb> material <SEP> textile <SEP> to
<tb>
 
 EMI8.9
 ¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ Polyamide base
 EMI8.10
 
<tb> 21 <SEP> m-methoxyphenol- <SEP> yellow-reddish
<tb>
 
 EMI8.11
 22 27 orange methoxyphenol
 EMI8.12
 
<tb> 23 <SEP> 3-methyl-5-pyrazolone <SEP> yellow
<tb>
<tb> 24 <SEP> 3-carbethoxy-5-pyrazolone <SEP> yellow
<tb>
 
 EMI8.13
 25 1-phenyl-3-methyl-5 - pyrazolone yellow 26 1- (21-ohlorophenyl) -3-methyl-5-PYrazolone yellow 27 l- (2'-tolyl) -3-meHiyl-5-pyrazolone yellow

 <Desc / Clms Page number 9>

 
 EMI9.1
 28 1 - (- trifluoromethylhenyl --3-methyl-5-.

   pyrazolone yellow 29 1-3 '- (N-methyl-rT- (3-hydroxethyl sulf ona- mido yellow) pheny17 -3-methyl-5-pyrazolone 30 1- (61-ohloro-21-tolyl) -3-methyl -5-pyra- reddish yellow
 EMI9.2
 
<tb> zolone-
<tb>
<tb> 31 <SEP> acetoacet-m-4-xylidide <SEP> yellow-greenish
<tb>
 EXAMPLE 32. -
The 10.9 parts of -cresol used in Example 20 are replaced by 16.1 parts of 2: 4-dihydroxyquinoline. A dye is obtained which dyes polyamide-based textiles in yellow-greenish tones of good washing strength.



  EXAMPLE 33 27.1 parts of 3-aminobenzene-sulfon-N- hydrochloride are nitrogenated.
 EMI9.3
 ((3 - chloroethyl) amide as in Example 1 and the resulting solution is added over 10 minutes to a solution of 15.3 parts of 2: 5-dimethoxyaniline a mixture of 200 parts of water and 10 parts of a 36% aqueous hydrochloric acid solution at a temperature between 0 and 5 C. After 12 hours, the insoluble product is filtered off and stirred in a mixture of 1200 parts of water and 25. parts of a 36% aqueous hydrochloric acid solution A solution of 6.9 parts of sodium nitrite in 50 parts of water at 10 ° C. is then added and the mixture is stirred for 4 hours.

   The resulting mixture is added to a solution of 9.4 parts of phenol and 16.0 parts of sodium carbonate in a mixture of 400 parts of water and 8 parts of a 32% aqueous solution of sodium hydroxide. sodium at a temperature of 0 to 5 C. The diazo compound thus obtained is separated by filtration, washed with water and dried. Dispersed in aqueous medium, it dyes polyamide-based textiles in orange tones with good wash fastness.



    EXAMPLE 34.-
27.1 parts of 3-aminobenzene-sulfon-N- (P-chloroethyl) amide hydrochloride are diazotized according to the method of Example 20 and the solution obtained.
 EMI9.4
 is added over 10 minutes to a solution of 18.1 parts of N: N-di (3-hydroxyethyl) aniline in a mixture of 200 parts of water and 10 parts of a 36% aqueous solution of hydrochloric acid at a temperature of 0 to 5 C. The mixture is neutralized with Congo red by adding 50 parts of a 30% aqueous solution of sodium acetate and after 12 hours the dye obtained is separated by filtration, washed with water and dried. Dispersed in an aqueous medium, it dyes polyamide-based textile materials orange with good wash fastness.



  EXAMPLE 35.-
 EMI9.5
 The 18.1 parts of N: N-di ((3-hydroxyethyl) aniline used in Example 34 are replaced by 19.5 parts of N: N-di (3-hydroxyethyl) m-, toluidine. 3- (µ-chloroethyl) aminosulfonyl-2'-methyl-4'-N: N-di (p-hydroxyethyl) aminoazobenzene is obtained, which dyes polyamide-based textile materials orange with good fastness to the light.



    EXAMPLE 36.-
Diazotized according to the method of Example 1, 27.1 parts of hydrochloride.
 EMI9.6
 4-aminobenzenesulfon-N- (p-ohloroethyl) amide drate and the solution obtained in 20 minutes is added to a solution of 19.9 parts of N-µ-cyanoethyl-a-naphthyl-amine in 800 parts of acetone at a temperature between 0 and 5 C. The mixture is stirred for 90 minutes and then neutralized with Congo red by slowly adding 25 parts of an aqueous solution at 30% of sodium acetate. The colo-

 <Desc / Clms Page number 10>

 The rant is filtered off, washed with water and dried. Dispersed in an aqueous medium, it dyes acetate rayon in orange tones and polyamide-based textiles in scarlet tones with very good wash fastness.

   The fixation of the dye on the textile material based on dyed polyamide reaches 68%.



  EXAMPLE 37.-
A solution of 6.9 parts of sodium nitrite in 50 parts of water is added to a solution of 27.1 parts of 2-aminobenzene-sulfon-N- (p-chloroethyl) amide hydrochloride in a mixture of 130 parts of acetic acid and 4 parts of a 36% aqueous solution of hydrochloric acid at a temperature between 10 and 15 cc The solution is stirred for 15 minutes and then added
 EMI10.1
 in 20 minutes to a solution of 19.5 parts of NsN-di ((3-hydrogyethyl) m-toluidi- ne in a mixture of 200 parts of water and 12 parts of a 36% aqueous solution of hydrochloric acid at a temperature of 0 to 5 C.

   The mixture is stirred for 2 hours, then neutralized with Congo bites by slowly adding 40 parts of a 30% aqueous solution of sodium acetate. The dye is filtered off, washed and dried. Dispersed in an aqueous medium, it dyes polyamide-based textile materials orange with excellent washing fastness and orange wool with good washing and fulling fastness.



  EXAMPLE 38.-.



   The 27.1 parts of 2-amino-benzenesulfon-N- (p-chloroethyl) amide hydrochloride used in Example 14 are replaced by 28.5 parts of hydrochloride.
 EMI10.2
 te of 2 - amino'benzenesulfon-N- (y-chloroprop-2'-yl) amide. A dye is obtained which dyes textile materials based on orange polyamide with very good washing fastness and orange wool with good washing and fulling fastness.



  EXAMPLE 39.-
A solution of 6.9 parts of sodium nitrite in 50 parts of water is added over 5 minutes. a solution of 30.1 parts of 4- hydrochloride
 EMI10.3
 aminobenzenesulfon-N (-chloro- (3-hydroxypropyl) amide in a mixture of 375 parts) of water and 15 parts of a 36% aqueous solution of hydrochloric acid at a temperature. temperature from 5 to 10 C. The solution thus obtained is added over 20 minutes at a
 EMI10.4
 solution of 19.5 parts of NsN-di (3-hydroxyethyl) -¯m-toluidine in 250 parts of water and 15 parts of a 36% aqueous solution of hydrochloric acid at a temperature of 0 to 5 C. After stirring the mixture for 2 hours, it was neutralized with Congo red by slowly adding 62.5 parts of a 30% aqueous solution of sodium acetate over 30 minutes.

   The insoluble product is separated. d by filtration, stirred for 30 minutes in 400 parts of water which has been made alkaline to sunflower by addition of sodium carbonate, separated by fil-
 EMI10.5
 tration, washed with water and dried. This gives 4- (T-chloro-j3-hydroxypropyl) amino-sulfon-2'-methyl-4'-N: N-di (p-hydroxyethyl) aminobenzene which has very good binding properties on textile materials. polyamide base and gives orange tones with good wash fastness.



  EXAMPLE 40.-
Diazotize 30.1 parts of 4-aminobenzene-sulfon-N- hydrochloride.
 EMI10.6
 (y-ahloro-p-hydroz.ypropyl) amide as in Example 39 and the solution thus obtained is added over 20 minutes to a solution of 10.8 parts -cresol in a mixture of 300 parts of water, 50 parts of a 2N aqueous solution of sodium hydroxide and 75 parts of a 2N aqueous solution of sodium carbonate at a temperature of 5 to 10 cc The mixture is stirred for 1 hour and the insoluble product is separated. by filtration, washed with water and dried. This gives 4- (r-chloro-
 EMI10.7
 p-hydroxypropyl) ainosulfon-2'-hydroXY-5'-methylazobenzene which dyes polyamide-based textiles in yellow tones with good wash fastness.



  EXAMPLE 41.-
A solution of 6.9 parts of sodium nitrite in 50 parts of water is gradually added to a suspension of 26.9 parts of 4-amino-3-chloro.

 <Desc / Clms Page number 11>

 
 EMI11.1
 benzenesulfon-N - (- chloroethyl) amide in a mixture of 400 parts of water and 25 parts of a 36% aqueous solution of hydrochloric acid at a temperature of 5 to 10 C. The suspension thus obtained is then added in 20 minutes to a solution
 EMI11.2
 tion of 19.6 parts of Np-cyanoethyl-a-naphthylamine in a mixture of 512 parts of acetone'- and 12 parts of a 36% aqueous solution of hydrochloric acid at a temperature of 0 to 5 C .

   The mixture is stirred for 2 1/4 hours, 68 parts of a 30% aqueous sodium acetate solution are added, the mixture is further stirred for 16 hours and 6 parts of the sodium acetate solution are added. sodium acetate. The precipitated dye is then filtered off, washed with water and dried. Dispersed in an aqueous medium, it dyes polyamide-based textile materials in red tones with excellent wash fastness.



   The following table gives the shade on polyamide-based textile materials of the dyes obtained by coupling 4-amino-3-chlo-
 EMI11.3
 robenzenesulfon-N - ((3 # chloroethyl) amide diazotized with the coupling elements shown in the second column of the table.
 EMI11.4
 
<tb>



  Example <SEP> Element <SEP> of <SEP> copulation <SEP> Grade <SEP> obtained <SEP> on <SEP> material <SEP> textile <SEP> to <SEP> base <SEP> of
<tb>
 
 EMI11.5
 ¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ Polyamide 42 N: N-di (j3-hydroxyethyl ) red cresidin
 EMI11.6
 
<tb> 43 <SEP> N-p-hydroxyethyl-N-p-cyanoethyl <SEP> orange
<tb> aniline
<tb>
 
 EMI11.7
 44 Nn-butyl-Np-hydroxyethyl-m-toluidine scarlet 45 Np-hydroxyethyl-alpha-naphthylamine brown 46 Np-hydroxyethyl-N-fi-cyanoethyl-m-tolui- reddish-orange dine 47 3-P: N-dimethylaminobenzenesulfon- N- orange-reddish
 EMI11.8
 
<tb> (p-chloroethyl) amide
<tb> 48 <SEP> N-p-hydroxyethyl-2-naphthylamine <SEP> red
<tb>
 
 EMI11.9
 49 N: N-di (P-hydr * ethyl) orange-reddish aniline 50 2-N:

  N-di (p-hydroxyethyl) amino-4-acetyl- bluish red
 EMI11.10
 
<tb> aminoanisole
<tb>
<tb> 51 <SEP> 2-ethoxy-1-naphthylamine <SEP> purple-reddish
<tb>
 
 EMI11.11
 52. 4-Chloro-1-N- (fi-hydroxyethyl) -naphthyl- bluish-red amine 53 5: 6: 7: 8-tetrahydro-1-N: N-di (p-hydroxy- orange ethyl) naphthylamine 54 N-3-ethoxy hyl - N --- cyanoethyl-¯m-tolu- orange
 EMI11.12
 
<tb> dine
<tb>
 
The following table gives the shades on polyamide-based textile materials of other dyes obtained by diazotizing the amines indicated in the second column of the table by copying the diazo compounds thus obtained with the coupling elements indicated in the third column of the whiteboard.



  The diazotization of the amines and the coupling with the coupling elements are carried out by the methods described in the preceding examples.

 <Desc / Clms Page number 12>

 
 EMI12.1
 
<tb>



  Example <SEP> Amine <SEP> Element <SEP> of <SEP> Grade <SEP> obtained <SEP> on
<tb>
<tb>
<tb>
<tb>
<tb> copulation <SEP> material <SEP> textile <SEP> to
<tb>
 
 EMI12.2
 ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ Polyamide 55 base 2-aminobenzenesulfon 3-methyl-5-PYrazolone yellow -N- ( (3-chloroethyl)
 EMI12.3
 
<tb> amide
<tb>
<tb>
<tb>
<tb> 56 <SEP> 2-anisidine-4-sulfon <SEP> N: N-di (p-hydroxyethyl) <SEP> orange
<tb>
<tb>
<tb> -N- (y-chloro-p-hydro- <SEP> -m-toluidine
<tb>
<tb>
<tb> xypropyl) amide
<tb>
 
 EMI12.4
 57 2-anisidine-4-sulfon N- (3-hydroxyethyl-1- red
 EMI12.5
 
<tb> -N- (p-chloroethyl) <SEP> naphthylamine
<tb> amide
<tb>
<tb> 58 <SEP> 3-aminobenzenesulfon <SEP> -cresol <SEP> yellow-greenish
<tb>
 
 EMI12.6
 -N- (y - chloro-p-hy- droxypropyl) amide 59 3-aminobenzenesulfon 3-hydrogy-: 8 benz-1: 2:

   red -N- (y-chloro-p-h- 3: 4-tetrahydroquinoline
 EMI12.7
 
<tb> droxypropyl) -N-methyl
<tb> -amide
<tb>
<tb>
<tb> 60 <SEP> 3-aminobenzenesulfon <SEP> 2-cresol <SEP> yellow
<tb>
 
 EMI12.8
 -N- (y-chloro-µ-hy-
 EMI12.9
 
<tb> droxypropyl) <SEP> aniline
<tb>
<tb> 61 <SEP> 3-aminobenzenesulfon <SEP> -cresol <SEP> yellow
<tb>
 
 EMI12.10
 -N- (2T-chlorocyçlo
 EMI12.11
 
<tb> hexyl) amide
<tb>
<tb> 62 <SEP> 4-aminobenzenesulfon <SEP> N: N-di (p-hydroxyethyl) - <SEP> orange
<tb>
 
 EMI12.12
 -N - ((3: 'y-dichloxo- m-toluidine
 EMI12.13
 
<tb> propyl) <SEP> amide
<tb>
<tb>
<tb>
<tb>
<tb> 63 <SEP> 2-amino-4-trifluoro <SEP> N:

  N-di (p-hydroxyethyl) - <SEP> scarlet
<tb>
<tb>
<tb>
<tb>
<tb> methylbenzenesulfon <SEP> m-toluidine
<tb>
<tb>
<tb>
<tb> -N- <SEP> (ss-chloroethyl)
<tb>
<tb>
<tb>
<tb> amide
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 64 <SEP> 2-amino-5-nitro- <SEP> N: N-di (p-hydroxyethyl- <SEP> violet-redâ-
<tb>
<tb>
<tb>
<tb> benzenesulfon-N- <SEP> m-toluidine <SEP> tre
<tb>
<tb>
<tb>
<tb>
<tb> (P-chloroethyl) -
<tb>
<tb>
<tb>
<tb>
<tb> amide
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 65 <SEP> 4-aminobenzene- <SEP> N: N-di (p-hydroxyethyl) - <SEP> orange
<tb>
<tb>
<tb>
<tb>
<tb> sulfon-N- (y-bro'- <SEP> m-toluidine
<tb>
<tb>
<tb>
<tb>
<tb> mo-p-hydroxypro-
<tb>
<tb>
<tb>
<tb> pyl) amide
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 66 <SEP> 4-aminobenzene- <SEP> N:

  N-di (p-hydroxyethyl) - <SEP> orange
<tb>
<tb>
<tb>
<tb>
<tb> sulfon-N- (p-bro- <SEP> m-toluidine
<tb>
<tb>
<tb>
<tb> moethyl) <SEP> amide
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 67 <SEP> p-nitroaniline <SEP> 2-naphthol-6-sulfon-N- <SEP> orange-red $ -
<tb>
<tb>
<tb>
<tb> (p-chloroethyl) amide <SEP> tre
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 68 <SEP> p-nitroaniline <SEP> 2-naphthol-6-sulfon-N- <SEP> orange-redâ-
<tb>
<tb>
<tb>
<tb> (y-chloro-p-hydroxypro- <SEP> tre
<tb>
<tb>
<tb>
<tb>
<tb> pyl) <SEP> amide
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 69 <SEP> -aminobenzene- <SEP> 2-naphthylamine-6-sulfon- <SEP> orange
<tb>
 
 EMI12.14
 sulfonamide N - ((3-chloroethyl)

  amide

 <Desc / Clms Page number 13>

 
 EMI13.1
 
<tb> Example <SEP> Amine <SEP> Element <SEP> of <SEP> Grade <SEP> obtained
<tb> copulation <SEP> on <SEP> material <SEP> tex-
<tb>
<tb> tile <SEP> to <SEP> base <SEP> of
<tb>
 
 EMI13.2
 ¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯¯¯ Polyamide
 EMI13.3
 
<tb> 70 <SEP> -nitroaniline <SEP> 3-N:

  N-diethylamino-ben- <SEP> red
<tb>
 
 EMI13.4
 zenesulfon-N- (P-chloro-
 EMI13.5
 
<tb> ethyl) <SEP> amide
<tb>
<tb>
<tb> 71 <SEP> 2-chloro-4-nitro- <SEP> "<SEP> red-blueâ-
<tb>
<tb>
<tb> aniline <SEP> tre
<tb>
<tb>
<tb>
<tb>
<tb> 72 <SEP> p-aminobenzene- <SEP> "<SEP> orange
<tb>
<tb> sulfonamide
<tb>
<tb>
<tb>
<tb> 73 <SEP> 3-chloro-4-amino- <SEP> "<SEP> scarlet
<tb>
<tb>
<tb> phenylethylsulfone
<tb>
<tb>
<tb>
<tb>
<tb> 74 <SEP> 2-amino-5-cyano- <SEP> "<SEP> red
<tb>
<tb> benzotrifluoride
<tb>
<tb>
<tb>
<tb>
<tb> 75 <SEP> 2-amino-5-nitro- <SEP> "<SEP> purple-redâ-
<tb>
<tb> benzonitrile <SEP> tre
<tb>
<tb>
<tb>
<tb>
<tb> 76 <SEP> 2-amino-5-nitro- <SEP> "<SEP> bluish red <SEP> <SEP>
<tb>
<tb> benzotrifluoride
<tb>
<tb>
<tb>
<tb>
<tb> 77 <SEP> 3-chloro-4-amino- <SEP> "<SEP> scarlet
<tb>
<tb>
<tb>

  phenyl-p-hydroxy-
<tb>
<tb> ethylsulfone
<tb>
<tb>
<tb>
<tb> 78 <SEP> 2-amino-5-nitro- <SEP> "<SEP> blue
<tb>
<tb>
<tb> thiazole
<tb>
<tb>
<tb>
<tb>
<tb> 79 <SEP> 4-amino-3-nitro- <SEP> 3-acetoacetylaminoben- <SEP> yellow
<tb>
 
 EMI13.6
 toluene zenesulfon-N- (fl-chloro-
 EMI13.7
 
<tb> ethyl) amide
<tb>
<tb>
<tb>
<tb> 80 <SEP> 3-aminobenzene- <SEP> -cresol <SEP> yellow
<tb>
<tb>
<tb> sulfon-N- (p-bro-
<tb>
<tb>
<tb> moethyl) <SEP> methyl-
<tb>
<tb>
<tb> amide
<tb>
 
 EMI13.8
 81 2-Naphthylamine-6- N:

  N di- (3-hydroxyethyl) orange
 EMI13.9
 
<tb> sulfon-N- (ss-chlo- <SEP> -m-toluidine
<tb>
<tb>
<tb> roethyl) <SEP> amide
<tb>
<tb>
<tb>
<tb> 82 <SEP> 2-aminobenzenesul- <SEP> N-p-hydroxyethyl-1- <SEP> red
<tb>
 
 EMI13.10
 fon N -. ((3 chloroethyl) naphthylamine
 EMI13.11
 
<tb> amide
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 83 <SEP> 2-anisidine-4-sul- <SEP> -cresol <SEP> yellow
<tb>
<tb>
<tb>
<tb>
<tb> fon-N- (ss-chloro-
<tb>
<tb>
<tb>
<tb>
<tb> ethyl) amide
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 84 <SEP> "<SEP> methyl-2-hydroxy-3- <SEP> red
<tb>
<tb>
<tb>
<tb>
<tb> nàphtoate
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 85 <SEP> 4-aminobenzenesul- <SEP> p-cresol <SEP> yellow
<tb>
<tb>
<tb>
<tb>
<tb> fon-N- <SEP> (p-y-dichlo-
<tb>
<tb>
<tb>
<tb> ropropyl)

  amide
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 86 <SEP> 2-amino-4-trifluo- <SEP> N-p-hydroxyethyl-1- <SEP> red-blueâ-
<tb>
<tb>
<tb>
<tb>
<tb> romethyl <SEP> benzene- <SEP> naphthylamine <SEP> ire
<tb>
<tb>
<tb>
<tb>
<tb> sulfon-N- (p-chloro-
<tb>
<tb>
<tb>
<tb>
<tb> ethyl) amide
<tb>
 

 <Desc / Clms Page number 14>

 
 EMI14.1
 
<tb> 87 <SEP> 4-aminobenzenesulfon- <SEP> -cresol <SEP> yellow
<tb>
<tb>
<tb> N- (p-bromoethyl) amide
<tb>
<tb>
<tb> 88 <SEP> 4-aminobenzenesul- <SEP> -cresol <SEP> yellow
<tb>
<tb>
<tb> fon-N- (p-chloro-
<tb>
<tb>
<tb> ethyl) amide
<tb>
 
 EMI14.2
 89 -aminobenzenesul- 2-nahtol-6-sulfon- orange
 EMI14.3
 
<tb> fonamide <SEP> N- (ss-chloroethyl)

  
<tb>
<tb> amide
<tb>
<tb>
<tb> 90 <SEP> 4-chloro-2-trifluo- <SEP> 2-naphthylamine-6- <SEP> orange
<tb>
<tb>
<tb> romethyl <SEP> aniline <SEP> sulfon-N- (ss-chloro-
<tb>
<tb>
<tb> ethyl) amide
<tb>
 
 EMI14.4
 The 2-anisidine-4-sulfon-N- (i-chloroethyl) amide used in the above examples can be obtained by treating acetyl-2-anisidine with chlorosulfonic acid and reacting the chloride of Acetyl-2-anisidine-4-sulfonyl with p-chloroethylamine in 10% aqueous acetone solution, mixed it! ge being kept neutral to sunflower by addition of sodium carbonate, filtering off the 2-anisidine-4-sulfon-N- (p-chloro-ethyl) amide which forms and heating it with a solution 15% aqueous hydrochloric acid at 80 C.

   The solution is then cooled and the hydrochloride of 2-anisidine-4-sulfon-
 EMI14.5
 N - ((3-chloroethylamide which separates is filtered off and dried.



  The 2-amino-4-tiifluoromethylbenzenesulfon-N- (fl-chlonoethyl) amide used in the above examples can be obtained by reacting 2-nitro-4-trifluoromethylahlorobenzene with sodium disulfide by passing chlorine. in an aqueous suspension of 2: 2-dinitro-4: 4'-di (trifluoromethyl) diphenyldisulfide thus obtained, by reacting the 2-nitro-4-trifluoromethylbenzenesulfonyl chloride thus obtained with p-chloroethylamine hydrochloride in aqueous medium in the presence of sodium carbonate and separating by filtration
 EMI14.6
 tion the 2-nitro-4-trifluorobenzenesulfon-N- (fl-chlonoethyl) amide which is formed.



  The nitro compound is then reduced to the state of the corresponding amino compound by hydrogenating an ethanol solution of the nitro compound in the presence of Raney nickel catalyst, filtering off the catalyst and evaporating the ethanol from the filtrate to obtain 2-amino-4-trifluoromethylbenzenesulfon-N- (P-chloroethyl) amide in the form of an oil.



   The 2-amino-5-nitrobenzenesulfon-N- (P-chloroethyl) amide used in the examples above can be obtained as follows:
A solution of 25 parts of ss-chloroethyl hydrochloride is added; mine in 50 parts of water by stirring to a solution of 40 parts of 4-nitroacetanilide 2-sulfonyl chloride (obtained by reacting 4-nitroacetanilide 2-sulfonic acid with a mixture of oxychloride of phosphorus and phosphorus pentachloride) in a mixture of 60 parts of acetone and 40 parts of water, which has been cooled to a temperature of 10 C. Then 170 parts of a 2N aqueous carbonate solution are added. sodium over 1 hour and the mixture is stirred for a further 20 hours, during which time the acetone
 EMI14.7
 evaporates.

   The precipitated 2-acetylamino-5-nitro-benzenesulfon N- (3-chloro-hyl) amide is then separated by filtration, washed with water and dried. A mixture of 20 parts of this compound, 38 parts of water, 50 parts of acetone and 27 parts of a 36% aqueous solution is stirred under boiling under a reflux condenser for 8 hours. 'hydrochloric acid. The solution is then cooled to 20 (and the yellow crystalline solid part is separated by filtration, washed with water and dried. This product has a melting point of 125 C.
 EMI14.8
 



  The 2-naphthol-6-sulfon-N - ((3-chloroethyl) amide used in the above examples can be obtained as follows:
Stirred at boiling under a reflux condenser for 12 hours

 <Desc / Clms Page number 15>

 
 EMI15.1
 a mixture of 23 parts of 2-hydroxy-1-naphthoic acid 6-sulfon-N- (p-ohloroethyl) amide (obtained by reacting 2-hydroxy-1-naphthoic acid 6-sulfochloride with ss-chloroethylamine in l (water in the presence of sodium carbonate), 54 parts of water, 38 parts of a 36% aqueous solution of hydrochloric acid and 80 parts of acetone. The solution is then cooled to 20 ° C. and the crystallized solid material obtained is separated by filtration, washed with water and dried.

   The product obtained has a melting point of 137 cc.
 EMI15.2
 The 2-Naphthylamine-6-sulfon-N- (fi-chloroethyl) amide used in the above examples can be obtained by reacting 2-aoetylaminonaphthalene-6-sulfonyl-6-ohloride with ss-chloroethylamine in water in presence of sodium carbonate by filtering off 2-acetylaminonaphthalene-6-sulfon-N-
 EMI15.3
 (fl-chloroethyl) amide which precipitates and on hydrolyzing the N-acetyl group by heating the resulting solid with an aqueous solution of hydrochloric acid.



  On cooling the solution, the product crystallizes out and is filtered off and dried.
 EMI15.4
 



  The 3-NsB-diethylaminobenzenesulfon-N- (p-ohloroethyl) amide used in the examples above can be obtained by heating a mixture of 126 parts of sodium diethyl metanilate and 583 parts of chlorosulfonic acid for 8 hours. at 100 C, pouring the mixture onto ice, filtering off the 3-N: N-diethylaminobenzene-sulfonyl chloride which precipitates and
 EMI15.5
 reacting this compound with (3-ch.oroethylamine in water in the presence of sodium carbonate. The precipitated solid is then filtered off, washed with water and dried.

   The product has a melting point of 62 C.
 EMI15.6
 The 3-aoetoaoetylaminobenzenesulfon-N- (p-ohloroethyl) amide used in the example above can be obtained as follows:
A mixture of 12.6 parts of dicon is stirred for 72 hours at 20 ° C.
 EMI15.7
 tone, 23.5 parts of 3-aminobenzenesulfon-N- (µ-athloroethyl.) amide and 150 parts of ss-ethoxyethanol, then 500 parts of water are added and the precipitated solid is separated by filtration, washed with water and it is dried. The product thus obtained has a melting point of 86 C.



    EXAMPLE 91.-
A solution of 6.9 parts of sodium nitrite in 50 parts of water is added to a solution of 26.5 parts of 2-anisidine-4-sul- hydrochloride.
 EMI15.8
 fon-N - ((3-chloroethyl) amide in a mixture of 600 parts of water and 15 parts of a 36% aqueous solution of hydrochloric acid, the temperature being maintained between 5 and 10 C by external cooling The solution thus obtained is stirred for 10 minutes, then added to a solution of 13.7 parts of oresidine in a mixture of 200 parts of water and 12 parts of a 36% aqueous solution of acid. hydrochloric acid at a temperature between 5 and 10 C.

   The mixture is stirred for 2 1/2 hours and a 30% aqueous solution of sodium acetate is added until the mixture is no longer acidic to Congo red. The amino monoazo compound thus obtained is then separated by filtration. The resulting solid is stirred with a mixture of 1000 parts of water and 25 parts of a 36% aqueous solution of hydrochloric acid. A solution of 6.9 parts of sodium nitrite in 50 parts of water is added, the temperature of the mixture being maintained between 5 and 10 ° C. by external cooling, and the mixture is stirred at this temperature for 17 hours.

   The solution thus obtained is then added to a solution of 12.4 parts of m-methoxyphenol, 28 parts of sodium carbonate, 40 parts of sodium acetate crystals and 4 parts of sodium hydroxide in 450 parts of water. at a temperature between 0 and 5 ° C. The mixture is stirred for 30 minutes and the precipitated disazo dye is filtered off, washed with water and dried. Dispersed in an aqueous medium, it dyes polyamide-based textile materials in red tones with excellent wash fastness.

 <Desc / Clms Page number 16>

 



  EXAMPLE 92-
Simultaneously added to a solution of 4.54 parts of 2-hydroxy-5-methyl-4'-aminobenzene in a mixture of 120 parts of acetone and 100 parts
 EMI16.1
 of water a solution of 5.7 parts of 3- (2'-ohloroethyl) benzoyl aminosulfonylchloride in 16 parts of water and 30 parts of an N aqueous solution of sodium carbonate, the temperature of the mixture being maintained at below 5 C by cooling. exterior housing. The mixture is then stirred for 20 hours while the acetone evaporates. The precipitated dye is filtered off, washed with water and dried. Dispersed in an aqueous medium, it dyes polyamide-based textiles in yellow tones with excellent wash fastness.



   The 3- (2'-chloroethyl) aminosulfonyl benzoyl chloride used in the example above can be obtained as follows:
Stirred at boiling under a reflux condenser for 16 hours a
 EMI16.2
 mixture of 20 parts of 3- (21-chloroethyl) amiiiosulfonyl-benzo-ic acid (obtained by reacting benzoic acid 3-sulfonyl chloride with ss-chl roethylamine), 13 parts of thionyl chloride and 80 parts of toluene. The mixture is then distilled under reduced pressure until 50 parts of distillate are obtained. The residual liquid is then cooled and the solid part which separates out by crystallization is filtered, washed with toluene and dried.

   The product obtained has a melting point of 82 this EXAMPLE 93.-
One part of the dye of Example 7 is dispersed in 20 parts of water and the dispersion thus obtained is added to 4000 parts of water containing 4 parts of a condensation product of ethylene oxide with an alcohol. fat. 100 parts of natural silk are placed in the dye bath thus obtained and the dyeing is carried out for 1 hour at 95 C. The natural silk is then removed from the dye bath, rinsed with cold water, then immersed for 15 minutes in an aqueous solution containing 0.2% of a condensation product of ethylene oxide with an alkylphenol and 0.2% of sodium carbonate which is heated to 60 C. The natural silk is then rinsed with water. water and dried.

   The natural silk is dyed scarlet having excellent fastness to wet treatments.



    EXAMPLE 94.-
Instead of 1 part of the dye of Example 19 used in Example 93, 1 part of the dye of Example 2 is used and instead of the 100 parts of natural silk 100 parts of a polyacrylonitrile fiber are used. modified) The fiber is dyed orange with excellent fastness to wet treatments.



  EXAMPLE 95.-
100 parts of polyamide-based textile material are immersed in a dye bath comprising 4000 parts of water and 5 parts of 2-amino-5-nitro-
 EMI16.3
 benzenesulfon-NL (µ-chloroethyl) amiàe and the dye bath is then heated to 85 ° C. for 1 hour. The polyamide-based textile material is then immersed for 30 minutes in a mixture of 4000 parts of water, 12 parts of sodium nitrite and 36 parts of a 36% aqueous solution of hydrochloric acid at 15 Ce The textile material polyamide base is then removed from the mixture and immersed for 30 minutes in a solution of 4 parts of 3-diethylaminoacetanilide hydrochloride in 4000 parts of water at 60 C.

   The polyamide-based textile material is then rinsed with water and treated for 30 minutes in a 0.2% aqueous solution of soap at 95 C. The polyamide-based textile material is colored purple which has a excellent resistance to wet treatments.



    EXAMPLE 9 6. -
 EMI16.4
 Instead of the 5 parts of 2-amino-5-nitro'benzenesulfon-N - ((3-chloroethyl) amide used in Example 95, 5 parts of 4-aminobenzenesul-

 <Desc / Clms Page number 17>

 fon-N- (ss-chloroethyl) amide which dyes the polyamide-based textile material in an orange tone having excellent fastness to wet treatments.



   The 100 parts of polyamide-based textile material used in the above example can be replaced by 100 parts of acetate-ray fabric which are then dyed orange having excellent fastness to wet treatments.



   CLAIMS.



   1.- New azo dyes insoluble in water, free from sulfonic acid, carboxylic acid and acylsulfonamide groups, and which do not contain more than one enolizable phenolic, hydroxyl or carbonyl group and which contain at least one group of the formula -SO2NRR 'each of which is directly attached to a different aryl ring present in the azo dye, characterized in that R represents a haloalkyl or halocycloalkyl radical, R' represents a hydrogen atom or a substituted hydrocarbon radical or not or a haloalkyl or haloalkyl or alternatively R and R 'are joined to form with the nitrogen atom a heterocyclic ring containing 1 halogen atom.



   2. - New water-insoluble azo dyes according to claim 1, characterized in that R represents an ss-chloroethyl radical and R 'a hydrogen atom.



   3. - New azo dyes insoluble in water according to claim 1, characterized in that R represents an ss-bromoethyl radical and R ′ a hydrogen atom.



     4.- New azo dyes insoluble in water of the formula
 EMI17.1
 where B represents the residue of a substituted or unsubstituted naphthalene benzene ring, D represents a substituted or unsubstituted amino group, X represents hydrogen or a halogen atom and Y a chlorine or bromine atom.



   5. - New azo dyes insoluble in water of the formula:
 EMI17.2
 where P represents a substituted or unsubstituted aryl or heterocyclic ring, Y a chlorine or bromine atom and Z and Z 'represent substituted or unsubstituted alkyl radicals which may be identical or different.

** ATTENTION ** end of DESC field can contain start of CLMS **.


    

Claims (1)

6.- New azo dyes insoluble in water of the formula: EMI17.3 where Y represents a chlorine or bromine atom and where the benzene rings may have substituents. <Desc / Clms Page number 18> 7.- New azo dyes insoluble in water of the formula: EMI18.1 where 1 represents a chlorine or bromine atom and the benzene rings may have substituents. 8. - Process for the preparation of new water-insoluble azo dyes according to claim 1, characterized in that an aromatic or heterocyclic amine is dinitrogenated and the diazo compound thus obtained is copulated with a coupling element, the aromatic amine. or heterocyclic and the coupling element being selected so that the azo dye obtained is free from sulfonic, carboxylic and acylsulfonamido groups, does not contain more than one enolizable phenolic, hydroxyl or carbonyl group and contains at least once one group of the formula -SO2NRR ', wherein R and R' are taken as defined in claim 1, each of these groups being attached to a different aryl ring present in the azo dye. 9.- Process for the preparation of novel water-insoluble azo dyes according to claim 2, characterized in that an aromatic or heterocyclic amine is dinitrogenated and the diazo compound thus obtained is coupled with a coupling element, the aromatic amine. or heterocyclic and the coupling element being chosen so that the azo dye obtained is free from sulfonic, carboxylic and acylsulfonamido groups, does not contain more than one phenolic, hydroxyl or enolizable carbonyl group and contains at least once a group of the formula: -SO2NRR 'where R represents a p-chloroethyl radical and R' represents a hydrogen atom each of which is attached to a different aryl ring present in the azo dye. 10.- Process for the preparation of novel water-insoluble azo dyes according to claim 3, characterized in that an aromatic or heterocyclic amine is dinitrogenated and the diazo compound thus obtained is coupled with a coupling element, the aromatic amine or heterocyclic and the coupling element being chosen so that the azo dye obtained is free from sulfonic, carboxylic and acylsulfonamide groups, does not contain more than one enolizable phenolic, hydroxyl or carbonyl group and contains at least once one group of the formula -SO2NRR ', where R represents a p-bromethyl radical and R' represents a hydrogen atom, each of these being attached to a different aryl ring present in the azo dye. II.- Process for the preparation of new water-insoluble azo dyes according to claim 1, characterized in that the corresponding azo compound containing one or more sulfonic acid groups is converted into sulfonyl chloride and then treated with a amine of the formula: HNRR 'where R and R' are taken in the sense indicated in claim 1. 12. - Process for the preparation of novel azo dyes insoluble in water according to claim 4, characterized in that dinitrogen an amine of the formula: EMI18.2 A diazo compound thus obtained with a coupling element of the formula: * -H-B-D where B and D are taken in the sense indicated in claim 4. <Desc / Clms Page number 19> 13.- Process for the preparation of novel azo dyes insoluble in water according to claim 5, characterized in that dinitrogenates an amine of the formula: -P-NH2, where P is taken in the sense indicated in claim 5 , and the diazo compound thus obtained is copulated with a coupling element of the formula: EMI19.1 where Y, Z and Z 'are taken in the sense indicated in claim 5. 14.- Process for the preparation of novel azo dyes insoluble in water according to claim 6, characterized in that dinitrogen an amine of the formula: EMI19.2 where Y is taken in the sense indicated in claim 6 and wherein the benzene ring may bear other substituents and the diazo compound thus obtained is copulated with a coupling element of the formula: EMI19.3 which copulates it in the ortho or -OH group position, the benzene ring possibly carrying other substituents. 15.- Process for the preparation of new azo dyes insoluble in water according to claim 7, characterized in that dinitrogen an amine of the formula: EMI19.4 wherein Y is taken in the sense indicated in claim 7 and wherein the benzene ring may bear other substituents and the diazo compound thus obtained is copulated with EMI19.5 a coupling element of the group: ci 6d- e 3. \ NI 6 where the benzene ring may have substituents. <Desc / Clms Page number 20> 16.- Process for the preparation of novel azo dyes insoluble in water as described above with reference to Examples 1 to 92. 17.- A method of dyeing textile materials, characterized in that one or more of the new water-insoluble azo dyes according to any one of claims 1 to 7 is applied to the textile materials. 18. A method according to claim 17, characterized in that the textile material is a textile material based on polyamide. 19.- Method for dyeing textile materials as described above particularly with reference to Examples 93 to 96. 20. - Textile materials colored with one or more of the water-insoluble azo dyes according to any one of claims 1 to 7.