Patent GB-365600-A (GB)
Title: Manufacture of new dyestuffs
IPC: C09B19/02
Filed: 1930-10-20
Abstract: Dyestuffs, which may be used for colouring lacquers and varnishes, are produced by halogenating products obtained by heating, either alone or in the presence of a high boiling solvent: (a) diarylaminohalogenated-1 : 4-benzoquinones, or (b) diarylaminobenzoquinones having the following formula: <PICT:0365600/III/1> in which X is hydrogen or halogen, R and R1 the same or different aryl residues, which with the nitrogen N1 may form a carbazol ring, and Y hydrogen, alkyl, or aralkyl.  By sulphonation, acid dyestuffs are obtained; these yield inorganic insoluble salts which may be used as lakes, and soluble salts with organic bases which may be used for colouring spirit lacquers, nitrocellulose lacquers and celluloid lacquers.  According to examples: (1) di-, tri-, and tetrabrom derivatives are obtained from the product produced by ring closure of 2 : 5-di (N-methyl (or ethyl) carbazolyl-3<1>-amino) 3 : 6-dichlor-1 : 4-benzoquinone, by direct bromination in nitrobenzene, sulphuric acid, or sulphuric acid saturated with potassium sulphate.  The brominated pigment dyes may be sulphonated with concentrated sulphuric acid.  (2) 2 : 5-di (N-benzyl-carbazolyl-3<1>-amino) 3 : 6-dichlor-1 : 4-benzoquinone is subjected to ring closure by heating, and is brominated in fluorsulphonic acid: (3) 2 : 5-di (b -naphthylamino)-3 : 6-dichlor-1 : 4-benzoquinone is subjected to ring closure and is treated in hot nitrobenzene with chlorine, in the presence of iodine.  The product is sulphonated with oleum. Specification 313,094, [Class 2 (iii), Dyes &c.], is referred to.  The Specification as open to inspection under Sect. 91 (3) (a) comprises also the halogenation of compounds having the general formula  <PICT:0365600/III/2> in which R is an aromatic or heterocyclic residue.  This subject-matter does not appear in the Specification as accepted.ALSO:Pigment dyestuffs are produced by halogenating products obtained by heating, either alone or in the presence of a high boiling solvent: (a) diarylaminohalogenated - 1 : 4 - benzoquinones, or (b) diarylaminobenzoquinones having the following formula: <FORM:0365600/IV/1> in which X is hydrogen or halogen, R and R1 the same or different aryl residues, which with the nitrogen N1 may form a carbazol ring, and Y hydrogen, alkyl or aralkyl.  The halogenation may be effected in the presence of halogenating catalysts, e.g. sulphur or antimony and of diluents, e.g. nitrobenzene, fluorsulphonic or sulphuric acids.  The products may be used as pigments for paper, wallpaper, varnishes and rubber. By sulphonation, acid dyestuffs are obtained; these yield inorganic insoluble salts which may be used as lakes, and soluble salts with organic bases which may be used for colouring spirit lacquers, nitrocellulose lacquers and celluloid lacquers. According to examples: (1) di-, tri-, and tetra-brom derivatives are obtained from the product produced by ring closure of 2 : 5-di-(N-methyl (or ethyl) carbazolyl-3<1>-amino) 3 : 6-dichlor-1 : 4-benzoquinone, by direct bromination in nitrobenzene, sulphuric acid or sulphuric acid saturated with potassium sulphate.  The brominated pigment dye may be sulphonated with concentrated sulphuric acid.  After washing, the dye is suitable for dyeing paper, wool, silk, cotton and viscose and mixed fabrics: (2) 2 : 5 - di - (N - benzylcarbazolyl - 3<1> - amino) 3 : 6-dichlor-1 : 4-benzoquinone is subjected to ring closure by heating, and is brominated in fluorsulphonic acid: (3) 2 : 5-di (b -naphthylamino)-3 : 6 - dichlor - 1 : 4 - benzoquinone is subjected to ring closure and is treated in hot nitrobenzene with chlorine, in the presence of iodine: the product is sulphonated with oleum. Specification 313,094, [Class 2 (iii), Dyes &c.], is referred to.  2 : 5 - Di - (N - benzylcarbazolyl - 3<1> - amino)-3 : 6-dichlor-1 : 4-benzoquinone and the corresponding N-methyl compound are prepared by condensing chloranil with 3 - amino-N-benzylcarbazol and 3-amino-N-methylcarbazol respectively.  3-Amino-N-benzylcarbazol may be made by benzylating 3-nitrocarbazol in alcoholic alkali solution and reducing the product. p  The Specification as open to inspection under Sect. 91 (3) (a) comprises also the halogenation of compounds having the general formula:  <FORM:0365600/IV/2> in which R is an aromatic or heterocyclic residue.  This subject-matter does not appear in the Specification as accepted.ALSO:Pigment dyestuffs which may be used for colouring rubber are produced by halogenating products obtained by heating, either alone or in the presence of a high boiling solvent: (a) diarylaminohalogenated-1 : 4-benzoquinones, or (b) diarylaminobenzoquinones having the following formula: <FORM:0365600/V/1> in which X is hydrogen or halogen, R or R1 the same or different aryl residues, which with the nitrogen N1 may form a carbazol ring, and Y hydrogen, alkyl, or aralkyl.  By sulphonation, acid dyestuffs are obtained; these yield inorganic insoluble salts witch may be used as lakes, and soluble salts with organic bases. According to examples: (1) di-, tri- and tetrabrom derivatives are obtained from the product produced by ring closure of 2 : 5-di (N-methyl (or ethyl) carbazolyl - 31 - amino) 3 : 6 - dichlor 1 : 4-benzoquinone, by direct bromination in nitrobenzene, sulphuric acid or sulphuric acid saturated with potassium sulphate.  The brominated pigment dyes may be sulphonated with concentrated sulphuric acid. (2) 2 : 5-di (N-benzyl-carbazolyl - 31-amino) 3 : 6 - dichlor-1 : 4-benzoquinone is subjected to ring closure by heating, and is brominated in fluorsulphonic acid: (3) 2 : 5-di (-b -naphthylamino)-3 : 6-dichlor-1 : 4-benzoquinone is subjected to ring closure and is treated in hot nitrobenzene with chlorine, in the presence of iodine. The product is sulphonated with oleum. Specification 313,094, [Class 2 (iii), Dyes &c.), is referred to.  The Specification as open to inspection under Sect. 91 (3) (a) comprises also the halogenation of compounds having the general formula:  <FORM:0365600/V/2> in which R is an aromatic or heterocyclic residue.  This subject-matter does not appear in the Specification as accepted.