Patent GB-367462-A (GB)
Title: Improvements in and relating to the production and use of benzanthrone derivatives
IPC: C07C45/67
Filed: 1930-08-25
Abstract: Benzanthrone derivatives containing selenium are made by the interaction of benzanthrone or its substitution products with selenium or a selenium compound.  The products may be treated with acid or alkaline condensing agents, or nitrating (followed by reduction if desired), halogenating, sulphonating, or oxidizing agents, or they may be condensed with alkyl or aryl halides or subjected to heat treatment, further products being thereby obtained. In examples (1) benzanthrone is treated with selenium dioxide in sulphuric acid to give a product containing selenium; on alkali-fusion this gives a vat dye dyeing in blue shades; (2) Bz1 : Bz1<1>-dibenzanthronyl selenide is obtained by treating Bz1-chlorbenzanthrone (a) with selenium or selenium dioxide in tetrahydronaphthalene in presence of sodium acetate, or (b) with selenium and calcium hydroxide in methylated spirit, with or without a copper catalyst; other acid absorbers, e.g. quicklime, barium hydroxide, sodium phosphate or sodium acetate may be used instead of calcium hydroxide; (3) Bz1 : Bz1<1>-dibenzanthronyl selenide is treated with chlorine in nitrobenzene in presence of a trace of iodine; the product, according to one of the Provisional Specifications, is a mixture of benzanthrone and chlorbenzanthrone; (4) Bz1 : Bz1<1>-dibenzanthronyl selenide is brominated at room temperature; the product appears to be a dibromobenzanthrone; (5) Bz1 : Bz1<1>-dibenzanthronyl selenide on alkali-fusion, or on treatment with aluminium chloride in pyridine, yields isodibenzanthrone; (6) Bz1 : Bz1<1>-dibenzanthronyl selenide is oxidized with hydrogen peroxide in sulphuric acid; the product, on alkali-fusion, dyes in a similar shade to that given by isodibenzanthrone; (7) Bz1 : Bz1<1>-dibenzanthronyl selenide is nitrated in the presence or absence of sulphuric acid or in nitrobenzene; one of the products is a tetranitro derivative which, on alkali-fusion, gives a vat dye dyeing in grey shades; (8) Bz1 : Bz1<1>-dibenzanthronyl selenide is sulphonated; (9) Bz1-benzanthronyl hydrogen selenide is obtained by treating Bz1-chlorbenzanthrone with selenium and caustic soda in methylated spirit; on treatment with dimethyl sulphate or iodobenzene the corresponding methyl- and phenyl-selenides are obtained: the latter yields isodibenzanthrone on alkali-fusion; (10) Bz1 : Bz1<1>-dibenzanthronyl selenide is obtained from Bz1-benzanthronyl hydrogen selenide (a) by heating to 300 DEG  C, (b) by heating with copper and nitrobenzene, (c) by heating with alcohol with addition of copper and lime, (d) by heating with selenious acid in nitrobenzene, or (e) by heating in sulphuric acid; (11) dichlorbenzanthrone (made by chlorinating Bz1-chlorbenzanthrone with sulphuryl chloride in nitrobenzene in presence of iodine) is treated with selenium to give a chlorinated dibenzanthronyl selenide, which, on alkali-fusion, gives a dye of the isodibenzanthrone type, and (12) nitro- and methoxy-Bz1-chlorbenzanthrones (examples (1) and (4) of Specification 256,281, [Class 2 (iii), Dyes &c.], on similar treatment yield amino-and methoxy-Bz1 : Bz1<1>-dibenzanthronyl selen ides, which also give dyes of the isodibenzanthrone type on alkali-fusion.