Patent GB-610808-A (GB)
Title: Improvements in anthraquinone acid dyestuffs
IPC: C09B1/20
Filed: 1944-12-21
Abstract: Anthraquinone acid dyestuffs are manufactured by condensing a halogen anthraquinone compound of the general formula <FORM:0610808/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 acid group, in the free acid or salt form, or one of them may represent hydrogen) with a mono- or di-amino heterocyclic o-biphenylene of the general formula R111-(NH2)m, wherein R111 represents a heterocyclic o-biphenylene radical of the general formula <FORM:0610808/IV (c)/2> (wherein Y is O, S, NH, N-alkyl or SO2) or a hydrogenated, alkyl, alkoxy, aryl, halogen or sulpho (e.g. sulphonic acid, sulphonamide or substituted sulphonamide) derivative thereof, and m is 1 or 2, in the presence of a copper condensation catalyst (e.g. copper powder or cupric or preferably cuprous salts, e.g. cuprous chloride), 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., especially at 75-85 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 and 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 useful 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 wool 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, formaldehyde - naphthalenesulphonic 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.  Examples (in which the "Ring Index" nomenclature is employed for the heterocyclic o-biphenylene compounds) describe the condensation of sodium 1-amino-4-bromoanthraquinone - 2 - sulphonate with: (1) 2 - amino - dibenzofurane, (2) 3-amino-2-methoxydibenzofurane, (3) 3-aminodibenzofurane, (4) 3-aminodibenzofurane - 8 - sulphodiethylamide, (5) 3 - aminocarbazole, (6) 3 : 6-diaminocarbazole, and (7) 2 : 7 - diamino - 3 : 6 - dimethylcarbazole; and also (8) of 1-amino-4-bromoanthraquinone-2-carboxylic acid with 3-aminodibenzofurane.  Lists of alternative starting materials are given.  Specifications 399,528, 409,014, 461,236, 461,237, 472,170, 474,999 and 495,790 are referred to.  The Specification as open to inspection under Sect. 91 comprises also the use of starting materials of the first general formula above in which X represents halogen (e.g. 1-amino-2 : 4-dibromoanthraquinone-5-, 6-, 7- and 8-sulphonic acids) and of amino heterocyclic o-biphenylene compounds in which the linking member Y is SO, and an alternative method of manufacture which consists in condensation of a mono- or di-amino heterocyclic o-biphenylene with a dihalogen aminoanthraquinone having an amine radical in the 1-position, a halogen atom in the 4-position and a second halogen atom in another (preferably the 2-) position, followed by replacement of the latter halogen by a sulphonate group by the action of a sulphite or bisulphite.  This subject-matter does not appear in the Specification as accepted.