Патент USA US3084163код для вставки
3,984,153 United States Patent 0 "ice 1 2 3,084,153 According to a further feature of the invention there is provided a process for the manufacture of the new water-insoluble azo dyestu?s, as hereinbefore de?ned, WATER-S?LUBLE MUNOAZO BENZOTHIAZQLE < idatented Apr. 2, 19%?» DYESTUFFS which comprises coupling a diazotised amine of the for Brian Ribbons Fishwiek and Eric Leslie Johnson, Man chester, England, assignors to Imperial Chemicai Indus 5 mula: ' tries Limited, London, England, a corporation of Great Britain No Drawing. Filed Oct. 28, 1959, Ser. No. 84§,l8*6 Claims priority, application Great Britain Nov. 3, 1958 3 Claims. (Cl. 260-158) 1O This invention relates to new azo dyestulis and more 7 S 1 particularly it relates to new water-insoluble azo dye wherein B and X have the meanings stated above, with stuifs which are valuable for the colouration of arti?cial a coupling component of the formula: textile materials. According to the invention there are provided the new 15 water~insoluble azo dyestuffs of the formula: wherein A, R and R’ have the meanings stated above. The process of the invention may be conveniently brought about by adding the amine to a solution of nitros ylsulphuric acid, adding the diazo solution so obtained to a solution of the coupling component in an aqueous wherein A represents a substituted or unsubstituted 1:4 25 solution of hydrochloric acid, adding sodium hydroxide and ?ltering off the azo dyestu? which is precipitated. phenylene or 1:4-naphthylene nucleus which is free from Those amines used in the process of the invention sulphonic acid and carboxylic acid groups, R represents wherein X represents a —CN group may be obtained by hydrogen or a substituted or unsubstituted lower alkyl treating the appropriate aminobenzonitrile with thiophos radical or aralkyl radical, R’ represents a substituted or unsubstituted lower alkyl radical, X represents a —-CN 30 gene, reacting the isothiocyanate so obtained with arm monia and ?nally treating the thiourea so obtained with or -—SCN group and the benzene ring B maybe further a solution of bromine in chloroform. substituted by groups other than sulphonic and carboxylic Those amines used in the process of the invention acid groups, provided that when R represents a [it-cyano wherein X represents a —SCN group may be obtained lower alkyl radical R’ does not represent either a ,B-cyano 35 by treating the appropriate aminothiocyanobenzene with or a ?-acyloxy-lower alkyl radical. a thiocyanate, for example sodium or ammonium thio As examples of the substituents which may be present cyanate and subsequently treating with chlorine or bro in the 1:4-phenylene or 1:4-naphthylene nucleus repre mine, or by treating the appropriate aminothiocyanoben sented by A there may be mentioned lower alkyl, such zene with thiophosgene, then with ammonia and ?nally as methyl, lower alkoxy such as methoxy, halogeno such as chloro and bromo, tri?uoromethyl and acylamino such 40 treating with bromine. As speci?c examples of amines which may be used as acetylamino. in the process of the invention there may be mentioned As examples of further substituents which may be pres ent in the benzene nucleus B there may be mentioned 2-amino-?-thiocyanobenzthiazole, lower alkyl, for example methyl, and halogeno for ex 45 2~arnino-6-cyanobenzthiazole, ample chloro and bromo. 2-amino-4-chloroeo-cyanobenzthiazole, As an example of an aralkyl radical represented by R 2-amino-4-bromo-6-cyanobenzthiazole, there may be mentioned benzyl. > 2-amin0-4methyl-G-thiocyanobenzthiazole, 2-arnino-4-ethyl-6-thiocyanobenzthiazole, 2-amino-6-methyl-4-thiocyanobenzthiazole, As examples of radicals which may be represented by both R and R’ there may be mentioned the lower alkyl radicals, methyl, ethyl, propyl and butyl and especially 2-amino-4-chloro-é-thiocyanobcnzthiazole and there may be mentioned substituted lower alkyl radicals, for example hydroXy lower alkyl radicals such as hy 2-amino-4-bromo~6-thiocyanobenzthiazole. droxyethyl, hydroxypropyl, hydroxybutyl, lower alkoxy As examples of coupling components which may be lower alkyl radicals such as ethoxyethyl, methoxyethyl, used in the process of the invention there may be men methoxypropyl, methoxybutyl, cyano-lower alkyl radi tioned cals such as cyanomethyl, cyanoethyl, cyanopropyl, cyanobutyl, acyloxy-lower alkyl radicals such as acetoxy N : N-bis ( B-acetoxyethyl) -m-toluidine, N: N-bis (?-hydroxyethyl) aniline, ethyl, acetoxypropyl, acetoxybutyl, propionoxyethyl, halogeno-lower alkyl radicals such as chloroethyl, bromo ethyl, carbo-lower alkoxy-lower alkyl radicals such as 60 carbethoxymethyl, carbomethoxyethyl, carbethoxyethyl, carbomethoxymethyl, lower Mkylsulphonyl-lower alkyl radicals such as methylsulphonylethyl, ethylsulphonyl ethyl, lower alkylcarbonyl radicals such as methylcar bonylethyl, ethylcarbonylethyl, and various other sub stituted lower alkyl radicals such as aminocarbonylethyl, dihydroxypropyl, 'y-chloro-?-hydroxypropyl, 'y-bromo-? hydroxypropyl, ?z'y-epoxypropyl, and ?-(4z6-diamino-s triazin-Z-yl) ethyl. N-B-cyanoethyl-N-B'-hydroxyethyl~m-toluidine, l~N-?-hydroxyethylnaphthylamine, Np’-cyanoethyl-N-B’-hydroxyethylaniline, N : N-bis- ( B-chloroethyL) aniline, N: N-bis- ( IS-carbethoxymethyb) aniline, N : N-bis- ( B-carbethoxyethyb) aniline, 65 N: N-bis- ( B-carbethoxyethyl- ) m-toluidine, N: N-bis- ( /3-methylsulphonylethyl-) aniline, N : N~bis~ ( ,B-methylcarb onylethyl- ) m-toluidine, N : N-bis»(y-chloro-?-hydroxypropyl-) aniline, N : N-bis-('y-bromo-?-hydroxypropyl-) aniline, 3,084,153 4 3 acterised by alkylating monoazo dyestuffs having no acid dissociating salt forming groups, of the general formula: N: N-bis-(?-v-epoxypropyh)m-toluidine, N-ethyl-N- ( ;8—hydroxyethy1-) aniline, N-n-butyl-N-B-cyanoethyl-m-toluidine, N-p-cyanoethyl-N-?'-methoxyethyl-m-toluidine, N-?-acetoxyethyl-N-;8’-carbethoxyethylaniline, R1 N N-y-chloro-?-hydroxypropyl - N - ?’-hydroxyethyl-m toluidine, 10 N-?-acetoxyethyl-N-?'-methylcarbonylethyl-m-toluidine, N-?-annnocarbonylethyl-N-ethylaniline, N-f3-y-dihydroxypropyl-N-ethylaniline, N-cyclohexyl-N-p-hydroxyethylaniline, N-benzyl-N-?-hydroxyethylaniline, N:N-bis-(?-carbomethoxyethyl-)-m-chloroaniline, N:N-bis-(p-acetoxyethyh)-m-acetylaminoaniline, N : N-bis- (p-acetoxyethyL) -m-tri?uoromethyl aniline, N-B-cyanoethyl-l-naphthylamine, N-y-chloro-?-hydroxypropyl-1-naphthylamine, dition that of R1 to R8 at least one R represents a sub stituent which does not dissociate acid in neutral water or that at least R9 or R10 represents a substituent with more than one carbon atom. Neither of these two speci?ca 20 tions describes the azo dyestuffs which are described in the present application. Compared with the nearest re lated dyestu?s described in British Patent No. 787,369 the dyestu?s of the present application are superior in respect of their a?'inity for textile materials comprising 25 cellulose acetate rayon and aromatic polyester ?bres. de?ned, are valuable for dyeing textile materials comprise ing arti?cial ?bres, for example cellulose ester ?bres such as cellulose acetate rayon and cellulose triacetate rayon, 30 adiparnide and the polymer from caprolactam, polyvinyl wherein R1 to R8 represent hydrogen or substituents which do not dissociate acid in neutral water, R9 and R10 repre cycle-aliphatic or aromatic substituents, wherein two The new water-insoluble azo dyestuifs, as hereinbefore polyamide ?bres such as ?bres from polyhexamethylene R11 15 neighbouring substituents R can form a ring with the con methoxybenzene, 1- [N-B-hyd roxyethylamino] -2-methoxy-5 -methylbenzene and R9 sent hydrogen, aliphatic, araliphatic, heterocyclic-aliphatic, 1- [N : N-bis- ( IS-hydroxyethyh) amino] -3-acetamido-6 1- [N-B-hydroxyethylamino] -5 -hydroxy-n aphthalene. / \ ' N-?-carbomethoxyethyl-N-?’-cyanotheyl-m-toluidine, N-ethyl-N-?-methylsulphonylethylaniline, N-?-carbomethoxyethyl-N-ethylaniline, Ila The invention is illustrated but not limited by the fol lowing examples in which the parts and percentages are by weight: Example 1 1.4 parts of sodium nitrite are added, with stirring, to 22 parts of sulphuric acid at a temperature between 20° and 27° C. during 30 minutes and the solution so ob ?bres such as polyacrylonitrile ?bres and modi?ed poly tained is stirred for a further 15 minutes. The solution acrylonitrile ?bres, and aromatic polyester ?bres such as is added with stirring to a suspension of 4.14 parts polyethyleneterephthalate ?bres. For dyeing such textile 35 of then 2-amino-6-thiocyano-benzthiazole in 34 parts of an materials it is preferred to use the new azo dyestuffs in a 85% aqueous solution of sulphuric acid, at a temperature ?nely dispersed form which may be obtained by milling of -3° C. 40 parts of water are then added and the the azo dyestu?fs with water in the presence of a dispersing mixture is stirred at 0° C. for 5 minutes. The diazo agent, for example the sodium salt of the condensation solution so obtained is then added to a solution of 5.58 product of formaldehyde and naphthalene-?-sulphonic 40 parts of N:N-bis-(?-acetoxyethyl-)m-toluidine in a mix acid. If desired the dispersed aqueous paste of the dye ture of 100 parts of water, 10 parts of a 2 N aqueous solu stuff so obtained may be dried to form a re-dispersible tion of hydrochloric acid and 50 parts of acetone at a powder which may be obtained in a non-dusting form by temperature of 5° C. 50 parts of a 40% aqueous solu any of the processes known for forming non-dusting pow tion of sodium hydroxide solution are then added, the mix ders. ture stirred for 30 minutes and the precipitated dyestu? The new azo dyestu?s, as hereinbefore de?ned, have .45 ?ltered oil. The dyestu? paste is stirred with 300 parts excellent at?nity for arti?cial textile materials which they of water, sodium carbonate is added until the mixture is dye in orange to greenish-blue shades possessing excellent neutral to litmus and the precipitated dyestuff is then fastness to light, washing and to dry heat treatments. ?ltered off, washed with water and dried. When dispersed The dyestuifs as hereinbefore de?ned wherein the sub stituent X occupies the 6-position of the benzthiazole nu 50 in aqueous medium the dyestutf dyes cellulose acetate, polyamide and aromatic polyester textile materials in cleus and wherein the benzene nucleus B is not further bluish-red shades possessing good fastness to light. The substituted or is further substituted only by halogen (for dyeings on aromatic polyester textile materials possess example chlorine) are of great value because of their excellent fastness to dry heat treatments. especially high ai?nity for arti?cial textile materials. Example 2 The dyestuifs as hereinbefore de?ned wherein at least 55 one of the radicals R and R’ is a substituted lower alkyl In place of the 5 .58 parts of N:N-bis-(?-acetoxyethyh) radical have especially high light fastness. m-toluidine used in Example 1 there are used 5.86 parts We have further found that the dyestuffs wherein one of NzN-bis-(B-carbethoxyethyl)aniline. The dyestuff so of the radicals R and R’ is a B-cyanoethyl radical or at obtained, when dispersed in aqueous medium, dyes aro least one of the radicals R and R’ is a ?-carbo-lower al 60 matic polyester textile materials in red shades possessing koxy-ethyl radical (for example a ?-carbethoxyethyl radi~ excellent fastness to light and to dry heat treatments. cal) are of particular value in the dyeing of polyethylene Example 3 terephthalate ?bres. Dyestuffs in which R and R’ repre In place of the 5.58 parts of N:N-bis(?-acetoxyethyl) sent ?-carbo-lower alkoxy-ethyl radicals or ,B-acyloxy-ethyl radicals wherein the acyl group is derived from a lower 65 rn-toluidine used in Example 1 there are used 4.14 parts alkyl carboxylic acid (for example a ?-acetoxyethyl radi of N-?-cyanoethyl-N-?'-hydroxyethyl-m-toluidine. The cal) are of particular value in the dyeing of cellulose ace dyestuft' so obtained, when dispersed in aqueous medium, dyes cellulose acetate and polyamide textile materials and British Patent No. 440,113 describes and claims a proc aromatic polyester textile materials in bluish-red shades ess for the manufacture of azo dyestuffs by coupling a 70 possessing excellent fastne‘ss to dry heat treatments. tate ?bres. diazotised Z-aminothiazole compound with an amine cou Example 4 pling in p-position to the amino group. In place of the 5.58 parts of N:N-bis-(?-acetoxyethyl-) British Patent No. 787,369 describes and claims inter m~toluidine used in Example 1 there are used 4.36 parts she a process for the production of water-soluble azo dyestu?s in which the azo dyestufI" forms the cation char 75 of N-,8-cyanoethyl-N-?-methoxyethyl-m~toluidinc. The 3,084,153 5 I 6 , listed in the second column of the table and coupling with the coupling components listed in the third column of the table by the method described in Example 1. product so obtained is (6-thiocyanobenzthiazol-Z-yl)-azo (2-methyl-4-N-?-cyanoethyl- N - ?-methoxyethylaminoben zene). When dispersed in aqueous medium it dyes aro matic polyester textile materials in red shades possessing outstanding fastness to light and to dry heat treatments. Example 5 Amine Coupling component textile material In place of the 4.14 parts of 2-amino-6-thiocyanobenz thiazole used in Example 1 there are used 3.5 parts of 2 2-amino-6-eyanobenz amino-‘G-cyanobenzthiazole and in place of the 5.58 parts thlazole. of N:N-bis(,8-acetoxyethyl-)m-toluidine there are used do _______________ .. 4.36 parts of N-B-cyanoethyl-N~?-methoxyethyl-m-tolui dine. The product so obtained is (6-cyanobenzthiazol-2 nobenzene) when dispersed in aqueous medium it dyes aromatic polyester textile materials in red shades possess ing outstanding vfastness to light and to dry-heat treat o ______________ __ In place of the 4.14 parts of 2-amino-6-thiocyanobenz— benzthlazole. thiazole used in Example 1 there are used 4.42 parts of do ______________ -_ Z-amino-4~thiocyano-6-methylbenzthiazole and in place of the 5.58 parts of N:N-bis-(B-acetoxyethyl)-m-toluidine 2-arnino-6~eyanobenz~ there are used 644 .parts of NzN-bis-(B-acetoxyethyl)-m 13.2 aminoacetanilide. The dyestuff so obtained, when dis persed in aqueous medium, dyes cellulose acetate, cel lulose triacetate and aromatic polyester materials in red _.___do ______________ ._ _-___do ______________ . In place of the 4.14 parts of 2-amino-6~thiocyanobenz thiazole used in Example 1 there are used 4.84 parts of 2-amino-4-chloro-6-thiocyanobenzthiazole and in place of the 5.58 parts of NzN-bis-(B-acetoxyethyl)-m-toluidine there are used 4.36 parts of N-?-cyanoethyl-N-B'-meth oxyethyl-m-toluidine. The dyestuff so obtained, when dispersed in aqueous medium, dyes cellulose acetate, cel 40 lulose triacetate and aromatic polyester textile materials in bluish red shades, possessing excellent fastness to dry heat treatments and good fastness to light. The 2~amino-4-chloro-6-thiocyanobenzthiazole is ob tained by treating an acetic acid solution of o-chloro aniline with 2 mol. equivs. of potassium th-iocyanate and 1 mol. equiv. of bromine, buffering the resulting mixture crystallisation from butanol. Example 8 in place of the 4.14 parts of 2-amino-6-thiocyanobenz~ idme. N : N-bis- (B-rnethoxy D0. Red. Red. ' Scarlet. Red. Red. Red. Reddish violet. Bluish red. Do. Do. Do. oxyethyD-m-tolu ethyl) -1n-t0lnidine. N: N-bis-(?-aeetoxy ethyl) -m-chlor0 aniline. _-___do ______________ __ N-?-cyanoethyl-N B’-carbethoxyethyl Red. m-toluidine. _-___do ______________ __ N :N-bis-(B-acetoxy Scarlet. _-___do ______________ __ N : N-bis-(B~acetoxy Reddish violet. 2-amino-6-eyanobenz thiazole. _-___do ______________ __ _.___do ______________ __ _.___do ______________ -. _ 2-amino6-thioeyano benzthiazole. __ - _ _do ______________ _ _ . __ - -do ______________ __ ethyD-rn-tri?uoro methylaniline. ethyl) -m~amino aeetanilide. N-?-eyanoethyl-m Orange. chloroaniline. N: N-bis-(carbometh oxymethyhaniline. N-cyanornethyl-N B-carbomethoxy ethylaniline. N-B-eyanoethyl-N B’-carbomethoxy ethylaniline. N :N-dimeth ylaniline _ Reddish orange. Do. Red. Bluish-red. NzN-bis-(carbethoxy Reddish-orange. methyl) aniline. N-methyl-N-B-(4: 6< diamino-s-triazin Red. 2-yl)ethylaniline. _-___do ______________ ._ N : N-bis- (B-methoxy Bluish red. _.___do ______________ __ N : N-bis-(B~acet0xy Red. ethyD-m-toluidine. ethyl) ~m-ehloro aniline. N-?-cyanomethyl-l naphthylamine. ethyl) -l-naphthyl Reddish violet. Violet-brown. amine. Red. N : N-bis- (B-acetoxy ethyD-l-naphthyl and the dyeings possess excellent fastness to dry heat treat ments and good fastness to light. Reddish-brown. amine. The 2-amino-4-chloro-6-cyanobenzthiazole is obtained _.___do .............. _. aniline with thiophosgene, treating the 2-chl01'o-4-cyan0 N: N-bis-(?-acetoxy ethyl) -rn-amino acetanilide. Bluish-red. N : N-bis- ('y-chloro-? D0. hydroxy-n-propyb m-toluidine. _-___do ______________ __ ring-closing the resulting N-(2-chloro-4-eyanophenyD using the dyestu?s obtained by diazotising the amines 75 N: N-dimethylaniline _-___do ______________ __ noacetanilide. The dyestu? so obtained, when dispersed in aqueous medium, dyes cellulose acetate, cellulose tri acetate and aroma-tic polyester materials in violet shades shades obtained on aromatic polyester textile materials N-ethyl-N-B-amino carbonylethyl N: N-bls-(B-carbeth are used 6.44 parts of N:N-bis-(?-acetoxyethyl)-m-ami thiourea by re?uxing with bromine in chloroform. The following table gives further examples of the N: N-bis-(B-amino earb onyle th yl) -m‘ toluidiue. _.___do ______________ __ Z-amino-4-chloro-6-cyanobenzthiazole and in place of the 5.58 parts of NzN-bis-(?-acetoxyethyl)-m-toluidine there phenylisothiocyanate so produced with ammonia, and 70 hydroxyethylaniline N-ethyl-N-B-carbo methoxyethyl aniline. N-n-butyl-N-B-cyano ethyl-m-toluidine. N : N-bis-(?-earb ethoxyethyD-m toluidine. N-B-hydroxyethyl N -,8’-aminocarbon ylethyl'rn-toluidine. N-n-butyl-N-B-cyano ethyl-m-toluidine thiazole used in Example 1 there are used 4.20 parts of by treating a chloroform solution of 2-chloro-4-cyano bis(?-hydroxy ethyl) aniline. N: N-bis(?-earheth oxyethyl) aniline. N-B-eyanoetl1y1-N-B _-___do ______________ __ _.___do ______________ _ with sodium acetate and treating with a further 2 mol. the precipitate by extraction with hot dilute acid and re oxyethyDm aniline. Example 7 equivs. of potassium thiocyanate and 1 mol. equiv. of bromine. The mixture is poured into water and the 2 50 amino-4-chloro~6~thiocyanobenzthiazole is isolated from 6. _.___do ______________ __ shades and the dyeings obtained possess excellent fast 30 ness to dry heat treatments and good fastness to light. Bluish-red. _.___do ______________ .. beéizthiazole. 20 N-?-eyanoethyl-N-B hydroxyethyl-m toluidine. 3 : 5-di1nethyl-N :N 2-amino-6-thioeyano Example 6 Yellowish—red. hydroxyethylaniline. _-___do ______________ _. _-___do ______________ __ ments. N—B-cyanoethyl-N-B toluidlne. N : N-bis-(?-acet yl)azo-(2-methyl-4-N-?ecyanoethyl-N-[i-methoxyethylami Shade on aro matic polyester _____do ______________ __ N : N-bis-(B-acetoxy ethyl) aniline. .____d0 ______________ __ _-___do ______________ __ N-B-cyanoethyl-m chloroanilina. Orange-brown. Red. Orange-brown. Orange.