Patent GB-670720-A (GB)
Title: Manufacture of substituted polycyclic quinones
IPC: C09B5/56
Filed: 1949-04-13
Abstract: Hydroxynitropolycyclic quinones are made by treating polycyclic quinones carrying at least two nuclear substituents selected from the class consisting of nitro and halogeno with a metal nitrite in an organic solvent or when the starting material contains at least one nitro group, optionally in a mixture of an organic solvent and water. Alkali metal, e.g. sodium and potassium, nitrites may be used. Polycyclic quinones specified are derivatives of anthraquinone and pyranthrone, representative being 2 : 3-dibromo-, 2-chloro-3-nitro-, 1 : 5-dinitro-, 1-chloro-8-nitro- and 1-bromo-4-nitro-anthraquinone, 4 : 10 - dibromoanthanthrone, 1 : 5-dichloro-4 : 8-dinitro-, 1 : 4 : 5-trichloro-and 1 : 5 - dinitro - 2 - methyl - anthraquinone and dibromopyranthrone and products obtained from some of them are specified.  Temperatures specified range from 20 to about 150 DEG C., according to the reactivity of the compounds.  Solvents specified are b -ethoxyethanol and dimethylformamide and p N-isopropyl-phthalimidine, c.f.  Specification 610,117.  Mixtures of solvents may be used.  A particular application is the production of 2-nitro-3-hydroxy-anthraquinone from 2 : 3 - disubstituted anthraquinones, other products specified being 1-nitro-5-hydroxy-, 1-nitro-8-hydroxy-, 4 : 5 : 8-trinitro - 1 - hydroxy-, 2 - nitro - 1 - hydroxy-, 2 - nitro - 6 - hydroxy -, 5 - chloro - 4 - nitro - 1 - hydroxy-, 5 - chloro - 1 - nitro - 4 - hydroxy-, 1 : 4 : 5 - dinitro - hydroxy-, 1 - nitro - 5 - hydroxy - and 5 - nitro - 1 - hydroxy - 2 - methyl - anthraquinones, 4-nitro-10-hydroxyanthanthrone and nitro-hydroxy-pyranthrone.  Mixed products are often obtained, e.g. 1-chloro-2-nitroanthraquinone gives mixed 1-nitro-2-hydroxy- and 2-nitro-1-hydroxyanthraquinones, but single products are obtained from symmetrically substituted polycyclic quinones.  In examples, sodium nitrite is used as nitrating agent and in (1) 1 : 5-dichloro- or 1-chloro-5-nitro-anthraquinone in dimethylformamide yield 5-nitro-1-hydroxy-anthraquinone; (2) 1 : 5-dichloro-4 : 8-dinitro- or 1 : 8-dichloro-4 : 5-dinitro-anthraquinone in dimethylformamide or aqueous b  - ethoxyethanol yields 4 : 5 : 8 - trinitro - 1 - hydroxyanthraquinone also obtained from 1 : 4 : 5 : 8 - tetrachloroanthraquinone in dimethylformamide; (3) 1 : 4-dichloro-, 1-chloro-4-nitro- or 1-bromo-4-nitroanthraquinone in dimethylformamide (or the last two compounds alternatively in aqueous b -ethoxyethanol) gives 1 - nitro - 4 - hydroxyanthraquinone; (4) 2 : 3-dichloro-, 2 : 3-dibromo- or 2-chloro-3-nitroanthraquinone in dimethylformamide (or the first two alternatively in tetramethylene or dimethyl-tetramethylene sulphone and the last in aqueous b -ethoxyethanol) yield 2-nitro-3-hydroxyanthraquinone; (5) 1 : 8-dichloro- or 1-chloro-8-nitroanthraquinone in dimethylformamide give 1-nitro-8-hydroxyanthraquinone; (6) dinitroanthraquinones in dimethylformamide or aqueous b -ethoxyethanol give mixed nitrohydroxyanthraquinones; (7) 1 : 5-dinitroanthraquinone in dimethylformamide gives 1-nitro-5-hydroxyanthraquinone ; (8) 1 : 8 - dichloro - 4 - nitro- or 1 : 5-dichloro-4-nitro-anthraquinone in b  - ethoxyethanol yield 5 - chloro - 4 - nitro - 1 - hydroxy- and 5-chloro-1-nitro-4-hydroxyanthraquinone; (9) 1 : 2-dichloro- or 1-chloro-2-nitro-anthraquinone in dimethylformamide probably give 2 - nitro - 1 - hydroxytogether with other nitro-hydroxy-anthraquinones; (10) 1 : 3-dichloroanthraquinone in dimethylformamide gives isomeric nitro-hydroxyanthraquinones and separation is effected after methylation with dimethyl sulphate to give compounds which are probably 1-nitro-3-methoxy- and 3 - nitro - 1 - hydroxyanthraquinones; (11) 4 : 10-dibromoanthanthrone in dimethyl-formamide gives 4-nitro-10-hydroxyanthanthrone; (12) 1-chloro-4 : 8-dinitro- and 1 : 4 : 5 - trichloroanthraquinone in dimethylformamide (or the former in aqueous b -ethoxyethanol) give mixed dinitrohydroxyanthraquinones; (13) dibromopyranthrone in dimethylformamide yield nitrohydroxypyranthrones; (14) 2 : 6-dichloroanthraquinone in dimethylformamide yield 2-nitro-6-hydroxyanthraquinone; and (15) 1 : 5-dinitro-2-methylanthraquinone in dimethylformamide yield nitrohydroxymethylanthraquinones.