Patent GB-327175-A (GB)
Title: Improvements in the manufacture and production of halogenated allo-ms-naphthodianthrones and condensation products thereof
IPC: C09B3/76
Filed: 1928-12-27
Abstract: 327,175. Johnson, J. Y., (I. G. Farbenindustrie Akt.-Ges.). Dec. 27, 1928. Addition to 303,184. Allo-ms-naphthodianthrone and their derivatives, other than iodo derivatives, are halogenated by treating them with chlorine or bromine or with both chlorine and bromine, or agents supplying these halogens, in inorganic acids at temperatures below 60‹ C., or in water or other inorganic suspending liquids, or with halogen under atmospheric pressure in the absence of suspending liquids. As inorganic acids, sulphuric acid, oleum, chlorsulphonic acid, phosphoric acid and perchloric acid are specified, while the other inorganic suspending media which may be used include melts of metal chlorides or mixtures thereof, such as mixtures of aluminium or iron chlorides with sodium chloride, and inorganic halogenating agents themselves, such as sulphuryl chloride, phosphorus oxychloride or mixtures thereof, such as a mixture of phosphorus oxychloride and phosphorus pentachloride. Chlorine and bromine may be brought into reaction either simultaneously or successively, and halogenating catalysts, such as sulphur, iodine, mercury, bismuth, antimony, selenium, phosphorus, iron, manganese, nickel, tungsten and molybdenum, may be employed, if desired. When halogenating in acid solution or in other inorganic liquids, partial or complete condensation to ms-anthrodianthrones may occur simultaneously with the halogenation. The products, which dye in orange yellow to blue red shades, are in part the same as those obtained according to the parent Specification and in part are new. They may be purified by the usual methods, such as by way of their oxonium salts, or by treating their aqueous pastes with oxidizing agents, such as hypochlorites, or by recrystallization from organic solvents, or by sublimation under reduced pressure. According to examples, (1) allo-ms-naphthodianthrone is treated with liquid bromine or with bromine vapour or gaseous chlorine, (2) an aqueous paste of allo-ms-naphthodianthrone is treated with bromine, (3) allo-ms-naphthodianthrone is treated with various amounts of bromine in chlorsulphonic acid in the presence of iodine or sulphur, (4) allo-ms-naphthodianthrone is heated with phosphorus pentochloride and phosphorus oxychloride, (5) mono-cyano-allo-msnaphthodianthrone (obtainable by treating with cuprous cyanide in pyridine or quinoline the mono-brom-allo-ms-naphthodianthrone made by brominating in nitrobenzene) is treated with chlorine or bromine in chlorsulphonic acid in presence of iodine, (6) a chlorobromo-allo-msnaphthodianthrone is obtained by treating alloms-naphthodianthrone with chlorine in chlorsulphonic acid, then adding sulphur and bromine to the reaction mixture, (7) monoamino-allo-msnaphthodianthrone (obtainable by condensing the monobrom derivative referred to in examples 5 with p-toluene-sulphamide and heating the product with an acid) is suspended in phosphoric acid and heated with bromine in presence of iodine; a similar product is obtained by treating with bromine in chlorsulphonic acid, and (8) monomethoxy-allo-ms-naphthodianthrone (obtainable by methylating the monohydroxy derivative obtained from the monoamino derivative by means of the diazo reaction) is treated with bromine in chlorsulphonic acid in presence of sulphur; a similar product, dyeing in blue red shades, is obtained by brominating diphenoxy-allo-msnaphthodianthrone (made by condensing dichlorallo-ms-naphthodianthrone with potassium phenolate) in sulphuric acid.