Patent GB-487705-A (GB)
Title: Improvements in the manufacture and production of compounds of the perylene series
IPC: C09B3/16
Filed: 1937-02-26
Abstract: Dyes are made by heating a reaction product of an acid halide and a benzanthrone with an unsaturated hydrocarbon, alcohol, alkyl halide, mercaptan, ether or thioether containing an aliphatic, aliphatic-aromatic or cycloaliphatic radicle of at least 6 carbon atoms in the presence of an acid condensing agent.  The starting materials, which are probably compounds of the dibenzanthrene or isodibenzanthrene series, are obtained from benzanthrone or its hydroxy, alkoxy, phenoxy, amino or alkyl derivatives, contain halogen, are not vattable and are converted by sulphuric acid into dibenzanthrone and isodibenzanthrones.  If benzanthrones having a free Bz.1-position are treated with the acid halide, dibenzanthrenes are obtained, but if the Bz.1-position is occupied by halogen or by a radicle of the formula -OR or -SR, R being alkyl, aralkyl, or aryl, isodibenzanthrenes are obtained. Condensing agents specified are the anhydrous halides of zinc, aluminium, iron or tin, and boron trifluoride.  Small amounts of basic substances or halogen hydracids are sometimes added, and as diluents may be used an excess of one of the reactants, or an aromatic hydrocarbon or a halogenbenzene.  The dyestuffs obtained dissolve in organic liquids (e.g. benzene) to give fluorescent solutions, and may be used for colouring and/or rendering fluorescent artificial resins of various kinds of hydrocarbons, paraffin and other waxes, oils, including mineral oils such as paraffin oil or benzine, fats, rubber and other natural and synthetic plastic masses as well as lacquers, including nitrocellulose lacquers.  In examples: (1) the reaction product from benzanthrone and benzoyl chloride is heated with dodecyl bromide and zinc chloride to give a deep red oil; the zinc chloride may be replaced by aluminium chloride, and the dodecyl bromide by dodecyl alcohol, octodecyl alcohol, abietinol, a mixture of dodecyl and tetradecyl alcohols, or by dodecyl ethers, or by olefines of high molecular weight; the benzanthrone starting material may be derived from derivatives of benzoyl chloride on the one hand, or on the other from 6-chlorbenzanthrone, Bz.1 - chlorbenzanthrone, Bz.1 - hydroxybenzanthrone, or Bz.1-thiocresylbenzanthrone; (2) the product from Bz.1-chlorbenzanthrone and oxalyl chloride is heated with zinc chloride and a mixture of dodecyl and tetradecyl alcohols in presence of hydrogen chloride to give a deep red oil; (3) the product from benzanthrone and oxalyl chloride is heated with dodecyl alcohol and zinc chloride; (4) Bz.1-brombenzanthrone, and phosphorus tribromide are reacted in dodecyl bromide, to give a powder which is insoluble in alkaline hydrosulphite and gives an isodibenzanthrone dyestuff on treatment with sulphuric acid; without isolating this intermediate, zinc chloride is added and the mixture heated; 6.Bz.1-dibromobenzanthrone may also be used; (5) Bz.1-brombenzanthrone is reacted with thionyl chloride in trichlorbenzene, followed by heating with dodecyl bromide and zinc chloride or iron chloride; (6) the product obtained by heating Bz.1-brombenzanthrone with stearic acid chloride in trichlorbenzene is heated with zinc chloride and octodecylene; (7) the product from 6-aminobenzanthrone and benzoyl chloride is heated with dodecyl bromide and zinc chloride; (8) the product obtained by warming 6-methylbenzanthrone with oxalyl chloride in nitrobenzene is treated as in (7); (9) the product from 2- (or 6- or 7-) chlorbenzanthrone and oxalyl chloride is treated as in (7); (10) the starting material of (1) is heated with dodecyl mercaptan or didodecyl sulphide and zinc chloride in presence of hydrochloric acid.