Patent GB-480162-A (GB)
Title: Improvements in the manufacture and production of compounds of the perylene series
Filed: 1936-07-13
Abstract: Hydrocarbons, in particular mineral oils such as paraffin oil and paraffin waxes are coloured and/or rendered fluorescent by condensation products obtained by heating dibenzanthrone or isodibenzanthrone or the corresponding leuco compounds or the ethers or esters of the latter, or hydroxy or mercapto derivatives of dibenzanthrone or isodibenzanthrone, or alkoxy- or alkylthiodibenzanthrones, or dibenzanthronyls, or ketonic or hydroxy or mercapto compounds of perylene or dinaphthyl, or perylene tetracarboxylic acid di-imides with aliphatic or cycloaliphatic unsaturated hydrocarbons containing at least six carbon atoms or aliphatic or cycloaliphatic alcohols, alkyl halides, mercaptans, ethers or thioethers having at least six carbon atoms in direct combination in the presence of a catalyst of the Friedel-Crafts type.ALSO:Condensation products are obtained by heating dibenzanthrone or isodibenzanthrone or the corresponding leuco compounds or the ethers or esters of the latter, or hydroxy or mercapto derivatives of dibenzanthrone or isodibenzanthrone, or alkoxy- or alkylthiodibenzanthrones, dibenzanthronyls, or ketonic or hydroxy or mercapto compounds of perylene or dinaphthyl, or perylene tetra-carboxylic acid di-imides with aliphatic or cycloaliphatic unsaturated hydrocarbons having at least six carbon atoms or high molecular weight aliphatic or cycloaliphatic alcohols, alkyl halides, mercaptans, ethers or thioethers having at least six carbon atoms in direct combination in the presence of a catalyst of the Friedel-Crafts type.  The hydroxy compounds may be prepared by hydrolysis of sulphonic acids or halogen compounds or by reduction of ketones; the mercapto compounds may be obtained by reduction of sulphonic acid halides.  Catalysts specified are the anhydrous halides of zinc, aluminium, iron, and tin, and boron fluoride or substances derived therefrom.  Halogen hydracids or little amounts of basic substances such as tertiary amines or alkali metal carbonates may be present.  Diluents specified are paraffin hydrocarbons and halogen benzenes, or an excess of one of the reactants; e.g. leucodibenzanthrone is heated with excess dodecylene, or dodecyl alcohol or dodecyl bromide in presence of zinc chloride while leading in hydrogen chloride.  Zinc dust may replace the zinc chloride when dodecyl bromide is used, zinc bromide being formed during the reaction.  Reactants of the second group specified are di-isobutylene, dodecyl mercaptan, dodecyl vinyl sulphide, octadecyl alcohol, and alcohols of the cyclohexane, hydronaphthalene, and terpene series.  The products are vividly coloured compounds soluble in organic liquids to fluorescent solutions, which may be used to render fluorescent artificial resins, hydrocarbons, paraffin waxes, oils, waxes, fats, mineral oils such as paraffin oil, rubber and other natural and synthetic plastic masses as well as lacquers.  They may be added to nitrocellulose lacquers.  In examples: (1) dibenzanthrone is heated with dodecyl alcohol in presence of anhydrous zinc chloride and dry hydrogen chloride; the dodecyl alcohol may be replaced by dodecylene or dihydroabietinol; (2) dodecyl alcohol is heated with dibenzanthrone in presence of zinc dust and hydrogen chloride; (3) dodecyl bromide is boiled with dibenzanthrone in presence of zinc dust and anhydrous sodium carbonate; dodecyl chloride may replace the dodecyl bromide, and the dibenzanthrone may be replaced by b z2.b z21 - dimethoxydibenzanthrone, b z2.b z21 - dihydroxydibenzanthrone, or b z2.b z21 - dimethyl - dithiodibenzanthrone; (4) leucodibenzanthrone is suspended in trichlorbenzene and heated with dodecyl bromide in presence of zinc chloride; (5) dodecyl bromide is heated with isodibenzanthrone or its 6.61-dichlor derivative in presence of zinc dust and sodium carbonate; (6) dodecyl alcohol is heated with the dodecyl ether of leucodibenzanthrone in presence of zinc chloride and hydrogen chloride; the dodecyl ether of leucodibenzanthrone may be replaced by the methyl ether; (7) dodecyl alcohol is heated with the benzoyl ester of leucodibenzanthrone in presence of zinc chloride and hydrogen chloride; (8) dodecyl vinyl sulphide is heated with dibenzanthrone in presence of zinc chloride; (9) dodecyl mercaptan is heated with dibenzanthrone in presence of zinc chloride and zinc dust; a deep red oil is obtained when hydrogen chloride is led into the reaction mixture; (10) dodecyl bromide is heated with perylene-3.10-quinone or dihydroxyperylene-3.10-quinone in presence of zinc chloride; (11) perylene tetracarboxylic acid di-imide is heated with dodecyl alcohol in presence of zinc chloride and zinc dust; (12) didodecylether is heated with dibenzanthrone and zinc dust, while leading in hydrogen chloride; didodecylether may be replaced by the methyl or ethyl ether of dodecyl alcohol; (13) didodecylsulphide is heated with dibenzanthrone in presence of zinc dust and hydrogen chloride; (14) dodecyl bromide is heated with 2.21-dibenzanthronyl and zinc chloride; (15) 1.11 - dinaphthyl-3.4.31.41-diquinone is heated with dodecyl bromide and zinc chloride.  Leuco-dibenzanthrone benzoyl ester is prepared by treating dibenzanthrone with benzoyl chloride and zinc dust in pyridine.  Didodecylether is obtained by reacting dodecyl bromide with sodium dodecylate.  Didodecylsulphide is prepared by heating dodecyl bromide with a solution of sodium sulphide in ethanol.