Patent GB-570561-A (GB)
Title: Improvements in the manufacture and use of azo dyes
IPC: C09B29/36
Filed: 1941-09-19
Abstract: Azo dyes of the general formula <FORM:0570561/IV/1> wherein R represents a residue of the benzene or naphthalene series, R1 represents H, alkyl, an unsaturated hydrocarbon group of a chain of not more than 5 carbon atoms, furfuryl or phenyl, R2, R3, R4 and R5 each represent H alkyl or phenyl, X represents O, S, SO or SO2, Z, Z1 and Z2 each represent H, hydroxyl, alkoxyl, esterified hydroxyl, alkyl or acylamino, at least one being a group -NYAcyl, wherein Y represents H, alkyl or phenyl, are obtained by diazotizing an amine R.NH2 and coupling with the appropriate component.  Specified alkyl groups include methyl, ethyl, propyl, butyl, b -hydroxyethyl, b -hydroxypropyl, b  : g -dihydroxypropyl, d -hydroxybutyl, b -methoxyethyl, b -ethoxyethyl, d -methoxybutyl, g -methoxypropyl, the corresponding acetoxyalkyl and propionoxyalkyl groups, b -chloroethyl, g -chloropropyl, b -iodoethyl, b -cyanoethyl, g -cyanopropyl, b -sulphoethyl, g -sulphopropyl, b -sulphatoethyl, g -sulphatopropyl, d -sulphatobutyl, b -phosphatoethyl, b - or g -phosphatopropyl, and carbamylalkyl groups.  Specified unsaturated hydrocarbon groups are the groups -CH2-CH=CH2, -CH2-CH2-CH=CH2, -CH2-CH=CH.CH3 and -CH2-CH2-CH2-CH=CH2.  Specified furfuryl groups are furfuryl itself, tetrahydrofurfuryl, 5-ethyl-furfuryl, 5 - ethyl - tetrahydrofurfuryl and 5-b -hydroxyethyl-tetrahydrofurfuryl. Specified phenyl groups are phenyl itself and phenyl substituted by chlorine or bromine atoms or by alkyl, hydroxyl, alkoxyl, cyano or nitro groups.  Specified acyl groups are formyl, acetyl, butyryl, lactyl, glycyl, lauryl, benzoyl, furoyl, tetrahydrofuroyl, carbamyl, the groups -SO2Y3, -SO2OY3, -P(OY3)2, -PO(OY3)2, wherein Y3 represents unsubstituted alkyl or phenyl, -C(NH).NH2, -C(NH).NH.C(NH).NH2 and -CO-(CH2)n-COOH, wherein n represents 1, 2, 3 or 4. Specified sulphonated diazo components are sulphanilic, metanilic, 4-nitroaniline-2-sulphonic, aniline-2 : 4-disulphonic, 2-chloroaniline-4-sulphonic, 1 : 3-, 1 : 4-, 1 : 5-, 1 : 6- and 2 : 8-aminonaphthalenesulphonic, 1 : 3 : 8- and 1 : 4 : 8-aminonaphthalenedisulphonic, 1 : 5 : 7-aminonaphtholsulphonic and 1 : 8 : 3 : 6-aminonaphtholdisulphonic acids.  The products free from nuclear sulphonic acid groups are especially suitable for the coloration of organic derivatives of cellulose and in some cases cotton, wool or silk, and those carrying nuclear sulphonic groups are suitable for the coloration of silk and wool and in some cases of cotton, nylon and viscose fibres.  Examples relate to the production of the dyestuffs, (1) 4-nitroaniline-2-sulphonic acid --> the cyclic sulphone from 7-acetylamino-thiophenmorpholine, which dyes silk and wool rubine; (2) 4 - nitroaniline --> 5 - glycollylamino - 1 - b  - hydroxyethyl - 3 - methyl - phenmorpholine, which dyes cellulose acetate artificial silk rubine; (3) 4 - nitro - 2 - chloroaniline --> 7 - N - dimethylglycylamino - 1 - b  : g  - dihydroxypropyl - 2 - methyl - 3 - ethyl - thiophenmorpholine, which dyes cellulose acetate artificial silk violet; (4) 4 - nitro - 2 - fluoroaniline --> 7 - N - methylcarbamylamino - 1 - b  - hydroxy - propyl - 3 - methyl - phenmorpholine, which dyes cellulose acetate artificial silk violet; (5) 5 - nitro - 2 - aminophenol --> the cyclic sulphoxide from 7 - N - methyl - methanesulphonylamino - 1 - b  - sulphoethyl - thiophen - morpholine (sodium salt), which dyes cellulose acetate artificial silk, wool and silk pinkish violet; (6) 2 : 4 - dinitroaniline --> 7 - tetra - hydrofuroylamino - 3 : 5 - dimethyl - 1 - g  - sul - phatopropyl - phenmorpholine (ammonium salt), which dyes cellulose acetate artificial silk, wool and silk reddish blue; (7) 6-bromo-2 : 4-dinitroaniline--> 5 : 7 - di - (acetylamino) - 1 - b  - methoxyethyl - 2 - n - butyl - thiophenmor - pholine, which dyes cellulose acetate artificial silk blue; (8) 5 - nitro - 2 - aminophenyl - methylsulphone --> 7 - n - caproylamino - 1 - carbamylmethyl-phenmorpholine, which dyes cellulose acetate artificial silk bluish purple; (9) 3 : 5 - dinitro - 2 - aminophenyl - methyl - sulphone --> 7 - laurylamino - 1 - b 11 - hydroxy - b 1 - ethoxy - b  - ethoxyethyl - thiophenmorpho - line, which dyes cellulose acetate artificial silk blue-green; (10) 3 : 5 - dinitro - 2 - aminobenzoic acid --> 7 - sulphoacetylamino - 1 - (41 - sulpho)benzyl - 2 - n - butyl - phenmorpholine, which dyes wool, silk, cotton, viscose and nylon fibres blue; (11) 1 : 8 : 3 : 6 - aminonaphthol - disulphonic acid --> 7 - benzoylamino - 1 - tetrahydrofurfuryl - 2 - methyl - phenmorpholine, which dyes wool, silk, cotton, viscose and nylon fibres blue; (12) and 13) 2 : 4-dinitroaniline - 6 - sulphonethylamide --> 7 - and 5 - acetylamino - 1 - b  - hydroxyethyl - 3 - methyl - phenmorpholines, which dye silk, cellulose acetate artificial silk and nylon fibres greenish-blue; (14) 6 - chloro - 2 : 4 - dinitroaniline --> 5 - acetylamino - 1 - b  : g  - dihydroxypropyl - 3 - methyl-phenmorpholine, which dyes silk, p  cellulose acetate artificial silk and nylon fibres blue.  The following compounds are also specified as coupling components, viz. the 7- or 8-acetylamino - 2 - methyl -, 7 - acetylamino - 2 - ethyl -, 7 - propionylamino - 2 : 5 - dimethyl - and 7 - furoylamino - 2 - methyl - phenmorpholines, 7 - acetylamino - 2 - methyl - thiophenmorpholine and 7 - acetylamino - 1 - b  - hydroxyethyl - 2 - ethyl - 5 - methoxy - phenmorpholine. Specification 548,903 is referred to.  The Specification as open to inspection under Sect. 91 comprises also examples of the production of the dyestuffs, (a) 3 : 5-dinitro-2-aminophenol --> 7 - guanidino - 1 - phosphatoethyl - 3-phenyl-thiophenmorpholine cyclic sulphone, (b) 4 - aminoazobenzene --> 7 - N - ethyl - acetylamino - 1 - ethyl - 2 - sulphophenyl - phenmorpholine, (c) 2 : 4 - dinitroaniline - 6 - sulphonic acid --> 7 - succinylamino - 1 - cetyl - 2 - sulphophenyl - thiophenmorpholine, (d) 4 - aminoacetophenone, 4 - nitro - 2 - chloroaniline, 2 : 4 - dinitroaniline - 6 - sulphonethyl - amide, 2 : 4 - dinitro - 6 - cyanoaniline, 1 - naphthylamine or its 4-nitro derivative or 5-nitro-2-aminoacetophenone --> 8 - N - phenyl - acetyl - amino - 5 - acetoxy - 1 - allyl - phenmorpholine, 8 - hydroxy - 7 - acetylamino - 1 - 41 - nitro - phenyl - thiophenmorpholine, 8 - methyl - 5 - acetylamino - 1 - b  - hydroxyethyl - phenmorpholine, 8 - guanidino - 5 - methoxy - 1 - methylthiophenmorpholine cyclic sulphoxide, 8-acetylamino - 7 - methoxy - 1 - b  - hydroxyethyl - 3 - methyl - phenmorpholine or 7 - methyl - 5 - propionylamino - 1 - b  - hydroxyethyl - phen morpholine.  The dyeing of casein fibres is also referred to.  This subject-matter does not appear in the Specification as accepted.  7 - and 8 - Acetylamino - 2 - methyl - phenmorpholines are obtained by reducing and hydrogenating in alcohol at 100-120 DEG  C. under pressure and in presence of a nickel catalyst, 2-nitro-4- and 3-acetylaminophenol acetonyl ethers, obtained by acetylating the product of reduction of the condensation product of chloroacetone with sodium 2 : 4- and 2 : 3-dinitrophenate respectively in presence of sodium iodide.  7 - Acetylamino - 2 - ethyl - phenmorpholine is similarly obtained from 2-nitro-4-acetylaminophenol-g -methylacetonyl ether, obtained by nitration of the product of acetylation of the product of reduction of the condensation product of chloromethyl-ethyl ketone with sodium p-nitrophenate in presence of sodium iodide.  7 - Propionylamino - 2 - 5 - dimethyl - phenmorpholine is similarly obtained from 2-nitro-4-propionylamino-6-methylphenol acetonyl ether, obtained by nitration of the product of propionylation of the product of reduction of the condensation product of chloroacetone with sodium 4-nitro-2-methyl-phenate in presence of sodium iodide.  7 - Furoylamino - 2 - methyl - phenmorpholine is similarly obtained from 2-nitro-4-furoylaminophenol acetonyl ether, obtained by treating with furoyl chloride the product of saponification of 2-nitro-4-acetylaminophenol acetonyl ether.  7 - Acetylamino-2-methyl-thiophenmorpholine is similarly obtained from 2-nitro-4-acetylaminothiophenol acetonyl thioether, obtained by reduction of 2 : 4-dinitrophenylmercaptoacetone obtained by the action of chloroacetone on 2 : 4-dinitrophenyl mercaptan.  7 - Acetylamino - 1 - b  - hydroxyethyl - 2 - ethyl - 5-methoxy-phenmorpholine is obtained by heating 7 - acetylamino - 2 - ethyl - 5 - methoxy - phenmorpholine with ethylene oxide in dioxane for 8 hours at 180 DEG  C. under pressure.  The cyclic sulphone from 7-acetylamino-thiophenmorpholine is obtained by oxidizing with potassium permanganate in acetone the product obtained by catalytic hydrogenation of the product of condensation, in presence of sodium iodide, of chloroacetaldehyde with 4-mercapto-3-aminoacetanilide, obtained by the action of sodium sulphide on 4-chloro-3-nitro-acetanilide.  5 - Glycollylamino - 1 - b  - hydroxyethyl - 3 - methyl - phenmorpholine is obtained by reaction successively of ethylene oxide, sodium hydroxide and ethyl glycollate on 5-acetylamino-3-methylphenmorpholine, obtained by catalytic reduction of the condensation product from a -chloropropionaldehyde and 2-nitro-6-acetylaminophenol, which is obtained by acetylating the product of reduction of 2 : 6-dinitrophenol with ammonium sulphide. 7 - N - dimethylglycylamino-1-b  : g  - dihydroxy propyl - 2 - methyl - 3 - ethyl - thiophenmorpholine is obtained by reaction of glycerol-a -monochlorhydrin with the product of catalytic reduction of 3 - (2 - nitro - 4 - N - dimethylglycylamino - thiophenoxy)-pentane-2-one, which is obtained by the action of dimethylamine on the product of condensation, in presence of sodium iodide, of 3-chloropentane-2-one with 4-mercapto-3-aminochloroacetanilide, obtained by the action of sodium sulphide on the product of chloroacetylation of 3-nitro-4-chloroaniline.  7 - N - methylcarbamylamino - 1 - b  - h