Patent GB-381265-A (GB)
Title: The manufacture of indophenols of the naphtho-carbazole series and of dyestuffs derived therefrom
IPC: C09B49/10
Filed: 1931-07-24
Abstract: Indophenols of the naphthocarbazole series are obtained by condensing a naphthocarbazole or a nitrogen or nuclear substitution product thereof containing a free p-position relative to the carbazolic imino group with quinonechlorimide.  The indophenols thus obtained may be reduced to the corresponding leuco compounds.  Both the indophenols and the leuco compounds may be treated with sulphurizing agents, especially with an alcoholic polysulphide solution of a high content of sulphur to give new dyestuffs dyeing vegetable fibres from a sodium sulphide bath or a vat greenishblue to green shades.  If the sulphurizing reaction is conducted in the presence of a suitable metal or metal salt, such as copper or a copper salt, dyestuffs are obtained giving more greenish shades.  In examples: (1) A solution of 1 : 2-benzocarbazole (a -naphthocarbazole) in sulphuric acid is treated with a solution of quinonechlorimide in sulphuric acid and the mixture is poured on to ice to separate an indophenol soluble in sulphuric acid, acetone, ether, and ethanol; the corresponding leuco-indophenol, obtained by reduction, such as with sodium hydrosulphite, may be treated with an alcoholic polysulphide solution to give a dyestuff dyeing cotton from the hydrosulphite vat greenish-blue shades; a similar, but more greenish, dyestuff is obtained by adding a copper salt to the mass.  (2) The N-ethyl derivative of 1 : 2-benzocarbazole replaces the 1 : 2-benzocarbazole in example (1) giving a sulphurized dye which dyes cotton from a sodium su phide bath pure green shades; the N-methyl homologue yields a similar dyestuff.  (3) 6-Methoxy-1 : 2-benzocarbazole replaces the 1 : 2-benzocarbazole in example.  (4) A solution of the sodium salt of the 3 : 4-benzocarbazole sulphonic acid of the formula <FORM:0381265/IV/1> in sulphuric acid is treated with a solution of quinone-chlorimide in sulphuric acid, poured on to ice and separated as the leuco compound by reducing the diluted solution with sodium hydrosulphite; the leuco body is then treated with a solution of sulphur, sodium sulphide, and copper sulphate in water to give a dyestuff dyeing cotton from a sodium sulphide bath blueish-black shades.  (5) 1 : 2-5 : 6-Dibenzocarbazole dissolved in sulphuric acid is treated with a solution of quinone-chlorimide in sulphuric acid and separated by pouring on ice.  It may be reduced according to known methods such as with sodium hydrosulphite to the corresponding leuco body and this may be sulphurized.  (6) 4<1>-Hydroxy-8-methyl-1 : 2-benzocarbazole dissolved in caustic soda solution is treated with a solution of quinonechlorimide in methanol and the indophenol is separated by acidifying the mixture and filtering.  N-Ethyl-1 : 2-benzocarbazole is prepared by treating potassium 1 : 2-benzocarbazole with ethyl bromide.  The N-methyl derivative is prepared in a similar manner.  6 - Methoxy - 1 : 2 - benzocarbazole is prepared from a -naphthol and 4-methoxyphenylhydrazine.  4<1> - Hydroxy - 8 - methyl - 1 : 2 - benzocarbazole is prepared by treating the compound formed by reacting o-tolylhydrazine with 1-aminonaphthalene-5-sulphonic acid with caustic soda.