Patent GB-470475-A (GB)
Title: Manufacture of dyestuffs and intermediate products
IPC: C09B5/04
Filed: 1936-02-14
Abstract: Intermediate products and dyestuffs are manufactured by reacting an a -halogenanthraquinone, which may contain further substituents, e.g. a further halogen atom, with monomethylhydrazine, and, if desired, treating the product, if it contains a reactive hydrogen atom attached to an amino residue, with an acylating agent.  The reaction is effected at raised temperature, preferably in the presence of a solvent or diluent, e.g. pyridine or amyl alcohol, and of a hydrogen halide binding agent, e.g. an alkali carbonate.  The products may be purified by crystallization, or by conversion into their salts with strong acids, or by treatment with alkali hypochlorite solution, and they may be converted into leuco-derivatives, e.g. leuco-sulphuric acid esters.  Those of the products which are dyestuffs may be used for dyeing and printing vegetable fibres, e.g. cotton, for colouring lacquers and plastic masses, or for dyeing artificial silk.  In examples: (1) 1-chloranthraquinone is heated with aqueous methylhydrazine in the presence of pyridine and calcined sodium carbonate; (2) 1-amino-5-chloranthraquinone is similarly treated; (3) 1-amino-4-chloranthraquinone is similarly treated; (4) the process of (1) is carried out in methyl alcohol instead of pyridine; (5) and (6) the product of (2) or (3) is treated with anthraquinone - 2 - carboxylic acid chloride or benzoyl chloride; (7) 4-amino-1 : 9-(N-methyl)-pyrazolanthrone, obtained by recrystallizing the product of (3) from pyridine, is treated with anthraquinone-2-carboxylic acid chloride; (8) 8-amino-1 : 9-(N-methyl)-pyrazolanthrone, obtained by reacting 1-amino-8-chloroanthraquinone with methylhydrazine, is similarly treated; (9) 5-amino-1 : 9-(N-methyl)-pyrazolanthrone, obtained as in (2), or the 4- or 8- amino derivative, is treated with 1 - chloro - anthraquinone - 2 - carboxylic acid chloride or 2-chloroanthraquinone-3-carboxylic acid chloride; (10) 1-chloro-4-benzoyl-aminoanthraquinone is heated with aqueous methylhydrazine in pyridine in the presence of sodium acetate; the product may be saponified with 90 per cent sulphuric acid, yielding 4 - amino - 1 : 9 - (N-methyl) - pyrazoanthrone; (11) 1 : 3-dibromanthraquinone is reacted with methylhydrazine as in (10), producing 1 : 9-(N - methyl) - pyrazol - 3 - bromanthrone; (12) 5 - amino - 1 : 9 - (N - methyl) - pyrazolanthrone is treated with the acid chloride obtained by reacting 1-aminoanthraquinone with isophthalic and chloride; (13) 1-chloranthraquinone - 2 - carboxylic acid is heated with aqueous methylhydrazine in the presence of calcined sodium carbonate and caustic alkali; (14) 4-amino-1 : 9-(N-methyl)-pyrazol-anthrone is heated in o-dichlorobenzene with a compound of the formula <FORM:0470475/IV/1> (obtainable by condensing anthraquinone-2-carboxylic acid chloride p  with toluene, oxidizing the methyl group by means of chlorine in nitrobenzene and converting the carboxylic acid into its chloride by means of phosphorus pentachloride); the product dyes cotton greenish-yellow shades; (15) 4-amino-1 : 9-(N-methyl)-pyrazolanthrone is acetylated by heating with acetic anhydride; (16) 5-amino-1 : 9-(N-methyl)-pyrazolanthrone is heated in o-dichlorobenzene with a compound of the formula <FORM:0470475/IV/2> (obtainable by reacting 1-chloranthraquinone with p-hydroxybenzoic acid and treating the product with phosphorus pentachloride); the product dyes cotton yellow shades; (17) cotton is dyed yellow with the product of (3) from an alkaline hydrosulphite vat; (18) acetate artificial silk is dyed greenish-yellow shades with the saponified product of (10), which is pasted with sulphite cellulose liquor or the sulphonation products from the residue of the distillation of benzaldehyde or turpentine oil and added to a soap solution.  The Provisional Specification comprises generally the treatment of an anthraquinone or a leucocompound thereof, containing in a -position an exchangeable group, with a hydrazine of the general formula XHN.NX.CH2X where X is hydrogen, alkyl, aralkyl or aryl, and the treatment of the products with agents for introducing substituents or condensing agents. Additional starting materials specified are on the one hand a -amino-, -hydroxy- and -alkoxyanthraquinones and their leuco-compounds, which may contain further substituents, e.g. alkyl, nitro, alkoxy or a minogroups or halogens, and on the other hand, dimethyl-, ethyl-, ethyldimethyl- and benzylhydrazines and their sulphates.  Reference is made to the oxidation of the products from leucoanthraquinones by means of air or nitrous gases; to the treatment of products containing halogen with aminoanthraquinones to produce anthrimides, which may be converted into carbazoles, e.g. by the action of sulphuric acid or pyridine-aluminium chloride; and to the treatment of the products with an aldehyde, e.g. formaldehyde, or a halogenating agent.