Patent GB-374487-A (GB)
Title: The manufacture of ketones of the anthraquinone series
IPC: C09B1/16
Filed: 1931-03-05
Abstract: A 5-or a -nitroanthraquinone-2-carboxylic acid halide is condensed with an aromatic compound containing a labile hydrogen atom in the nucleus such as benzene, chlorobenzene, m-xylene, diphenyl, diphenyleneoxide, diphenylether, naphthalene, acenaphthene and N-alkylcarbazoles, in the presence of a catalyst such as aluminium or ferric chloride in accordance with the Friedel-Crafts reaction.  The nitroketones thus formed may be reduced to amino compounds and these may be acylated in order to obtain dyestuffs.  If a technical mixture of the 5- and 8-nitroanthraquinone-2-carboxylic acid halides be employed as starting material the products may be separated into their components at any stage.  In example (1) a mixture of 5- and 8-nitroanthraquinone-2-carboxylic acid chlorides or the pure 5- or 8-nitroanthraquinone-2-carboxylic acid chloride and diphenyl is dissolved in nitrobenzene, a solution of aluminium chloride in nitrobenzene added thereto and the mixture of 5- and 8-nitro-2-anthraquinonyldiphenylketone isolated by adding petroleum and filtering.  The nitroketone thus formed may be reduced by sodium sulphide to give an aminoketone which can further be condensed with acyl chlorides or halogen anthraquinones to give dyestuffs.  The mixture of aminoketones obtained by starting from the mixture of 5- and 8-nitroantraquinone-2-carboxylic acid chlorides are separated by dissolving in trichlorobenzene and filtering off at 100 DEG  C. the 5-amino-2-anthraquinonyldiphenylketone and then the 8-amino compound separates from the cooled filtrate, advantageously after the addition of petrol.  The 5-amino-2-anthraquinoxyldiphenylketone gives a reddish-brown solution and the 8-amino compound a violet-brown solution in sulphuric acid mixed with formaldehyde.  The benzoyl derivative of the 5-amino compound from an olive-green vat and the benzoyl derivative of the 8-amino compound from a reddish-violet vat both dye cotton yellowish-green.  It is possible to start from a mixture of the 5- and 8-nitroanthraquinone-2-carboxylic acids and effect the formation of the acid chlorides and the condensation as a single operation.  The diphenyl used may be replaced by diphenyloxide (example 4).  In example (2) aluminium chloride is added to a suspension of 5-(8)-nitroanthraquinone-2-carboxylic acid chloride in chlorobenzene and the resulting suspension poured into acidified water the precipitate thus formed being filtered and washed with water and alcohol.  The mixture of 5- and 8-nitro - 2 - anthraquinonyl - 4<1> - chlorophenylethers is moistened with alcohol and reduced with sodium sulphide giving a compound soluble in sulphuric acid with an orange-yellow shade turning chestnut on the addition of formaldehyde.  In example (3) aluminium chloride is added to a mixture of 5-(8)-nitroanthraquinone-2-carboxylic acid halide, 1 : 3-dimethylbenzene and carbon bisulphide and the mass worked up as in example (2) to give a compound which on reduction yields 5-(8)-amino-2-anthraquinonyl - 2<1>-4<1>-dimethylphenylketone. Specification 16271/10, [Class 2 (iii), Dyes &c.], is referred to. 5-Nitroanthraquinone-2-carboxylic acid chloride and 8-nitroanthraquinone-2-carboxylic acid chloride are separated from mixtures thereof by dissolving in sulphuric acid and fractionally precipitating.