Patent GB-476988-A (GB)
Title: Manufacture of heterocyclic compounds of high molecular weight
IPC: C09B1/26
Filed: 1937-04-20
Abstract: Heterocyclic compounds of high molecular weight containing cyclically-bound keto groups are manufactured by reacting an o-dicarboxylic anhydride, e.g. phthalic anhydride or its substitution products, with a pyrenoline or chrysenoline in the presence or absence of an indifferent solvent or diluent and preferably in the presence of a condensing agent, e.g. an aluminium halide or ferric chloride, if desired in the presence of an addition which lowers the melting point, such as an alkali halide, e.g. sodium or potassium chloride or a mixture thereof. Those products containing substituents replaceable by reaction with amines, e.g. halogen, may be condensed with p  aminoanthraquinones, or the products may be halogenated, e.g. with chlorine or bromine, and the halogen derivatives may be condensed with aminoanthraquinones.  The anthraquinonylamino derivatives may be carbazolized.  The products, which are intermediates or dyes suitable for dyeing and printing vegetable fibres, may be purified by recrystallization from high boiling solvents, e.g. nitrobenzene or trichlorobenzene, by conversion into their salts with strong acids, or by treatment with oxidizing agents, e.g. alkali hypochlorite.  They may be converted into leuco derivatives, e.g. leuco-sulphuric esters.  In examples: (1) 3-pyrenoline (obtained by the action of glycerol and sulphuric acid on 3-aminopyrene in the presence of nitrobenzene) is baked with phthalic anhydride and aluminium chloride; the product is probably monophthaloyl-3-pyrenoline; (2) a mixture of aluminium, sodium and potassium chlorides is used as condensing agent in the process of (1); (3) 3-pyrenoline is heated with phthalic anhydride and aluminium chloride in the presence of tetrachlorethane to produce 3 - pyrenolinoyl - o - benzoic acid, which is baked with aluminium chloride; (4) 3-pyrenoline is heated with phthalic anhydride in the presence of trichlorobenzene with gradual addition of aluminium chloride; (5) the product of (1) is treated with sulphuryl chloride in nitrobenzene in the presence of iodine; the product dyes cotton in a green-blue vat red shades; (6) bromine is employed in place of the sulphuryl chloride in (5); the product dyes cotton in a green-blue vat red shades; (7) 3-pyrenoline is baked with 3 : 6-dichlorophthalic anhydride and aluminium chloride, yielding 3<1> : 6<1> - dichloromonophthaloyl - 3 - pyrenoline, which dyes cotton in a green vat red shades; (8) 4-bromophthalic anhydride similarly yields 4<1> - bromomonophthaloyl - 3 - pyrenoline, which dyes cotton from a blue-green vat bluish-red shades; (9) the product of (8) is treated with sulphuryl chloride in nitrobenzene in the presence of iodine; the product dyes cotton in a blue-green vat red-blue shades; (10) the product of (8) is heated with 1-aminoanthraquinone, nitrobenzene, cuprous chloride and anhydrous sodium acetate; the product dyes cotton in a green-olive vat Bordeaux shades; (11) the product of (8) is similarly reacted with 1 - amino - 4 - benzoylaminoanthraquinone; the product dyes cotton in an olive vat violet shades; (12) the product of (10) is heated with pyridine and aluminium chloride; the product dyes cotton in an olive-green vat brown shades; (13) 2-chrysenoline (obtained by the Skraup synthesis) is baked with phthalic anhydride and aluminium chloride; the product dyes cotton in a wine-red vat yellow shades; (14) and (15) cotton is dyed red shades with the product of (1) in alkaline hydrosulphite vats.