Patent GB-182031-A (GB)
Title: The manufacture of new colouring matters
Filed: 1921-08-30
Abstract: Oxyalkylated oxazines, azines, and thiazines are obtained by applying the standard reactions for the preparation of oxazines, azines, and thiazines, to intermediates containing one or more oxyalkyl groups attached to nitrogen.  The products are suitable for conversion into sulphate colours as described in Specification 181,750, and are usually more soluble than the corresponding alkylated bodies.  The general reactions are described and are illustrated by the following examples:-  Oxazines.-A dyestuff dyeing chromed wool purple is obtained from gallamide and nitrosooxyethyl-o-toluidine and a dyestuff dyeing chromed wool blue from gallic acid and nitroso-oxyethyl-ethylaniline; other nitroso-oxyalkyl aromatic amines may similarly be condensed with gallic acid, gallamide or gallanilide: Celestine Blue is condensed with asym-dioxyethyl-p-phenylene diamine in presence of dinitrobenzene; other alkylated or oxyalkylated gallocyanines may similarly be condensed with asym-dioxyalkyl- or oxyalkyl-alkylm- or p-diamines, or oxyalkylated gallocyanines may be condensed with primary arylamines or phenols; nitroso-diethyl-m-aminophenol is condensed with oxyethyl-a-naphthylamine and the dye isolated as the zinc chloride compound; it dyes tannined cotton similarly to Nile Blue 2B : nitroso-dioxyethyl-m-aminophenol is condensed with benzyl-a-naphthylamine or oxyethyl-a-naphthylamine, or a-naphthylamine, to form very soluble blue dyes; in the same way nitroso-dioxyethyl-m-amino-p-cresol may be condensed with the above a-naphthylamine derivatives: b -naphthol is condensed with nitrosooxyethyl-o-toluidine, the product dyeing redder shades than Meldola's blue.  Azines.-Products dyeing tannined cotton scarlet to red shades are obtained by condensing nitroso-oxyethyl-o-toluidine with 4-p-tolylamino-2-amino-1-methylbenzene or its benzyl derivative; in the same way nitroso oxyalkyl-alkyl-aniline may be condensed with 4-p-tolylamino-2-toluidine or an alkyl, benzyl, or oxyalkyl derivative thereof, on a nitroso derivative of ethyl-o-toluidine, dimethyl- or diethyl-aniline can be condensed with an oxyalkylated 4-p-tolylamino-2-toluidine.  Basic violet to purple dyestuffs are obtained from the following pairs of components:-nitrosodimethyl-aniline and sym-dioxyethyl-m-phenylene diamine, or sym-dioxyethyl-m-toluylene diamine, or sym-di(dioxypropyl)-m-phenylene diamine; nitrosodiethylaniline and sym-dioxyethyl-m-toluylene-diamine; nitroso-oxyethylaniline and sym-dimethyl-m-phenylene diamine; nitrosophenol and sym-dioxyethyl-m-phenylene diamine. Specifications 6176/95 and 9794/95 are referred to.  Thiazines.-A reddish blue basic dye is obtained by reducing with zinc dust nitrosooxyethyl-o-toluidine, oxidizing the p-diamine together with sodium thiosulphate and then oxidizing further with oxyethyl-o-toluidine; it is isolated as the zinc chloride compound; other oxyalkyl asym-p-diamines can be similarly condensed with oxyalkyl- or alkyl-arylamines, or asym-dialkyl-p-diamines may be condensed with oxyalkylarylamines. Oxyalkylated amines are obtained as described in Specification 13956/04 by treating the parent amines with chlorhydrins in aqueous solution in presence of chalk.  Oxyethyl-a-naphthylamine, sym-dioxyethyl-m-phenylene diamine, dioxyethyl-m-aminophenol, and sym-dioxyethyl-m-toluylenediamine are thus obtained from the parent amines and ethylene chlorhydrin.  Sym-di (dioxypropyl)-m-phenylenediamine is similarly obtained from glycerol monochlorhydrin.  Asym-dioxyethyl-p-phenylene diamine is obtained by boiling acetyl-p-phenylenediamine with aqueous ethylenechlorhydrin, and saponifying. Nitroso-oxyalkylarylamines.-Nitroso-oxyethyl-o-toluidine, nitroso-dioxyethyl-m-aminophenol, nitroso - oxyethylaniline, nitroso-oxyethyl-ethylaniline, and nitroso-dioxyethyl-m-amino-p-cresol are obtained by treating the parent amines with sodium nitrite and acid.  Oxyalkylated-p-diamine thiosulphonic acids may be obtained from nitroso-oxyalkylarylamines and sodium thiosulphate in the usual manner; the treatment of nitroso-oxyethyl-o-toluidine, and nitroso-oxyethyl-ethylaniline is described.