Patent GB-575285-A (GB)
Title: Process for the production of 4-ketone and 4-sulphone derivatives of naphthasultone 1:8-naphthol sulphonic acid and 1:8-naphthol sulphonamide
IPC: C07D327/02
Filed: 1943-10-20
Abstract: 4-Ketone and 4-sulphone derivatives of 1 : 8-naphthasultone are obtained by condensing 1 : 8-naphthasultone with a carboxylic acid halide or a sulphonic acid halide in presence of aluminium chloride. Advantageously, a water-free solvent such as nitro-benzene, trichlorobenzene, chloroform or petroleum ether is used and the condensation may be followed by saponification with an alkaline agent to produce the corresponding 1 : 8-naphtholsulphonic acid derivative or with ammonia or an ammonia-yielding agent to produce the corresponding 1 : 8-naphtholsulphonamide derivative.  In examples: (1) 1 : 8-naphthasultone is heated with acetyl chloride or bromide in trichlorobenzene in presence of aluminium chloride to form 1 : 8 - naphthasultone - 4 - methyl - ketone which is saponifiable to the disodium salt of 1-hydroxy naphthalene-4-methyl-ketone-8-sulphonic acid by boiling with aqueous sodium hydroxide or is convertible into the ammonium salt of 1-hydroxynaphthalene-8-sulphonamide-4-methyl-ketone by shaking with aqueous ammonia and thence into the free sulphonamide by dissolving in dilute soda lye and acidifying with mineral acid; if the acetyl halide is replaced by butyryl chloride, the corresponding 4-propyl ketone compounds are obtained; (2) 1 : 8-naphthasultone is heated with isovaleryl chloride in trichlorobenzene in presence of aluminium chloride to form 1 : 8 - naphthasultone-4-isobutyl ketone similarly saponifiable to the disodium salt of 1-hydroxynaphthalene-4-isobutyl ketone-8-sulphonic acid (which salt may be reconverted into the naphthasultone by boiling with phosphorus oxychloride) or convertible to the ammonium salt of 1-hydroxynaphthalene-8-sulphonamide-4-isobutyl ketone by heating with aqueous ammonium carbonate; (3) 1 : 8-naphthasultone is heated with benzoyl chloride or bromide in trichlorobenzene in presence of aluminium chloride to form 1 : 8-naphthasultone - 4 - phenyl - ketone similarly saponifiable to the disodium salt of 1-hydroxynaphthalene-4-phenylketone-8-sulphonic acid; (4) 1 : 8-naphthasultone is heated with 4-nitrobenzoyl chloride in trichlorobenzene in presence of aluminium chloride to form 1 : 8-naphthasulton - 4 - (41 - nitrophenyl) - ketone similarly saponifiable to the disodium salt of 1-hydroxynaphthalene - 4 - (41 - nitrophenyl) - ketone - 8 - sulphonic acid and thence into the mono-sodium salt by treatment with hydrochloric acid or into the corresponding 41-aminophenyl compound by reduction; the 4-nitrobenzoyl chloride may be replaced by 4-chloro-3-nitrobenzoyl chloride to obtain the corresponding 41-chloro-31-nitrophenyl ketone compounds; (5) 1 : 8-naphthasultone is heated with 4 - methyl - benzene-1-sulphochloride in trichlorobenzene in presence of aluminium chloride to form 1 : 8-naphthasultone-4-(41-methylphenyl)-sulphone which is convertible as in (1) to the disodium salt of 1 - hydroxy - naphthalene - 4 - (41 - methylphenyl)-sulphone-8-sulphonic or to 1-hydroxynaphthalene - 8 - sulphonamide - 4 - (41 - methylphenyl)-sulphone.