Patent GB-626446-A (GB)
Title: Improvement in anthraquinone acid dyestuffs
IPC: C09B1/32
Filed: 1944-12-21
Abstract: 2-Ethyl-1-hexanol is used to inhibit foaming in the preparation of a dyestuff by heating together sodium 1-amino-4-bromoanthraquinone-2-sulphonate and 4-aminobiphenyl-41-sulphocyclohexylamide in aqueous ethylene glycol monoethyl ether in the presence of sodium carbonate, cuprous chloride and the surface-active agent " Nacconol NR."  Specifications 381,954, 399,528, 454,959, 461,236, 461,237, 474,999, 475,386 and 495,790, [all in Group IV], are referred to.ALSO:Aminobiphenylsulphonamides of the general formula <FORM:0626446/IV (b)/1> (wherein R111 represents the residue of biphenyl with the amino and sulphonamide groups attached to the same benzene nucleus or to different nuclei, and R1V and RV may each represent hydrogen or an alkyl, aralkyl, hydroxyalkyl, cycloalkyl, aryl, hydroaryl or heterocyclic radical or may jointly form with the amido-nitrogen atom a heterocyclic ring) are prepared by condensing the corresponding acylamino-(e.g. acetamido-) or nitro-biphenylsulphonyl halide with ammonia or an amine of the formula NHR1VRV and then hydrolysing the acylamino group or reducing the nitro group.  Specifications 381,954, 399,528, 454,959, 461,236, 461,237, 474,999, 475,386 and 495,790 are referred to.ALSO:Anthraquinone acid dyestuffs are manufactured by condensing a halogen anthraquinone compound of the general formula <FORM:0626446/IV (c)/1> (wherein R1 and R11 may each represent hydrogen or an alkyl, aralkyl, hydroxyalkyl, cycloalkyl, aryl, hydroaryl or heterocyclic radical, and X and Z may each represent a carboxylic or sulphonic group, in the free acid or salt form, or one of them may represent hydrogen) with an aminobiphenylsulphonamide of the general formula <FORM:0626446/IV (c)/2> (wherein R111 represents the residue of biphenyl with the amino and sulphonamide groups attached to the same benzene nucleus or to different nuclei, and RIV and RV may each represent hydrogen or an alkyl, aralkyl, hydroxyalkyl, cycloalkyl, aryl, hydroaryl or heterocyclic radical or may jointly form with the amido-nitrogen atom a heterocyclic ring) in the presence of a copper condensation catalyst (e.g. powdered copper or cupric or preferably cuprous salts) and advantageously of an acid-binding agent (e.g. sodium carbonate or acetate), preferably in an aqueous medium (which may also contain a water-soluble organic solvent, e.g. methyl or ethyl alcohol, diethylene glycol or dioxane) at about 70-100 DEG  C.  The products may be recovered by acidification of the reaction mixture and filtration, and may be purified by washing with dilute acid or hot saline solution or by repeated dissolution in water or alcohol or a mixture thereof and crystallization in the form of the sodium salt.  In the latter form they dye nylon (e.g. in the form of masses, sheets, rods, fibres or textiles) and animal or other proteinic fibres (e.g. wool, silk, azlon or soya bean fibres) in blue to green shades from acid or preferably neutral baths, especially those containing sodium sulphate, these last being particularly suitable for dyeing mixed fabrics (e.g. nylon-rayon or nylon-cotton) with the simultaneous use in the same bath of direct dyestuffs for rayon or cotton, whilst union shades on mixed fabrics of nylon and animal or other proteinic fibres may also be produced from neutral baths.  By treating the dyestuffs in aqueous solution with a water-soluble salt or other compound of a metal other than one of the first group of the periodic table (e.g. barium, tin, lead, aluminium, calcium, strontium, magnesium, copper, chromium or nickel) they are converted into lakes, which dye animal fibres and nylon from aqueous dispersions.  The dyestuffs may be employed in conjunction with diluents and assistants (e.g. dextrine, sugars, sodium chloride or sodium hexametaphosphate) or dispersing agents (e.g. higher alkyl aryl sulphonates, diarylmethane sulphonates, formaldehydenaphthalenesulphonic acid condensation products, "Tamol NNO" or mixtures of alkyl benzene sodium sulphonates derived from kerosene), and they may be marketed in the form of powdered compositions containing such additions.  In examples: (1) sodium 1-amino-4-bromoanthraquinone-2-sulphonate is heated with 4-aminobiphenyl-41-sulphodiethylamide in aqueous alcohol in the presence of urea, sodium bicarbonate and cuprous chloride; (2) the same anthraquinone compound is heated with 4- aminobiphenyl-41-sulphodiethanolamide in aqueous alcohol in the presence of sodium carbonate and cuprous chloride, and the reaction mixture is rendered slightly acid and treated with aluminium formate to precipitate the aluminium lake; alternatively the free acid is precipitated with hydrochloric acid, filtered off and redissolved in aqueous sodium carbonate solution and the sodium salt is salted out; (3) the same anthraquinone starting material is heated with 4-aminobiphenyl - 41 - sulphocyclohexylamide in an aqueous solution of ethylene glycol monoethyl ether in the presence of sodium carbonate, cuprous chloride, "Nacconol NR" and 2-ethyl - 1 - hexanol; (4) 1 - amino - 4 - bromoanthraquinone-2-carboxylic acid is heated with 4 - aminobiphenyl - 41 - sulphodiethylamide in water in the presence of soda ash, copper sulphate and cuprous chloride.  Lists of alternative reactants are given.  Specifications 381,954, 399,528, 454,959, 461,236, 461,237, 474,999, 475,386 and 495,790 are referred to.  The Specification as open to inspection under Sect. 91 comprises also an alternative method of preparing certain of the dyestuffs, which consists in condensing the aminobiphenylsulphonamide with a dihalogen aminoanthraquinone having an amine radical in the 1-position, a halogen atom in the 4-position and another halogen atom elsewhere in the anthraquinone nucleus (e.g. 1-amino-2 : 4-dibromoanthraquinone-5-, 6-, 7- or 8-sulphonic acid) and treating the product with a sulphite or bisulphite.  This subject-matter does not appear in the Specification as accepted.