Patent GB-380082-A (GB)
Title: Improvements in the treatment of organic substances with sulphurising agents
Filed: 1931-04-27
Abstract: Organic substances are fused with sulphur and alkali or alkaline sulphide in the presence of oxidizing substances which do not enter into the molecule of the sulphurized organic substance and have the formula XNO2 in which X indicates a metallic element or an aliphatic or aromatic hydrocarbon radicle such as nitrobenzene, ethyl nitrite or nitrites of alkali metals or of alkaline earth metals.  In examples (1) Phenol, aqueous caustic soda or sodium sulphide and sulphur are heated together and sodium nitrite is added slowly.  (2) b -Naphthol is fused with aqueous caustic soda and sulphur and sodium nitrite is slowly added giving a product which, when dissolved in aqueous caustic soda and precipitated therefrom by means of acid, consists of a di-naphthol thioether.  (3) Inspissated sulphite cellulose waste liquor is heated with sulphur, aqueous caustic soda and sodium nitrite to give a tanning agent.  (4) Rapeseed oil, linseed oil, acids thereof or other drying vegetable oil is heated with caustic soda solution, sulphur and sodium nitrite to give a factice.  (5) 2 : 4-Dinitrophenol heated with sulphur and sodium sulphide in the presence of sodium nitrite gives a red brown product soluble in alkalies.  (6) Ethyl alcohol is boiled with sodium sulphide and sulphur to form a polysulphide and p-hydroxyphenyl - 3 - aminocarbazole is then added; solid sodium nitrite is added, and a blue dyestuff separates out from which free sulphur may be removed by extraction with aqueous sodium sulphide or a suitable organic solvent such as carbon disulphide.  (7) p-Hydroxy-3-amino-9-ethylcarbazole replaces the amino carbazole used in the previous example and the sodium nitrite is added in solution.  (8) 4-Amino-3-methyl-4<1>-hydroxydiphenylamine is heated with sodium sulphide and sulphur, a solution of sodium nitrite in water is added and the whole further heated; the melt is finally diluted with water and the dyestuff precipitated with dilute acid or airblown.  (9) Methylcyclohexanol, sodium sulphide and sulphur are heated together and p-hydroxydiphenylamine slowly added; a mixture of nitrobenzene and methylcyclohexanol is then added, the mass diluted with water and slightly acidified and the remainders of nitrobenzene and the methylcyclohexanol distilled off by steam to yield a dyestuff. (10) 4-Phenylamino-4<1>-hydroxydiphenylamine replaces the p-hydroxydiphenylamine used in example (9) and the nitrobenzene is added alone.  Specifications 26448/01, 15763/05, [both in Class 2, Acids and salts, Organic &c.], 25246/11, 15752/14, 111,738, 186,107, 243,739, [all in Class 2 (iii), Dyes &c.], 283,233, [Class 91, Oils &c.], 335,297, [Class 2 (iii), Dyes &c.], 359,254, 359,273, 359,276 and 362,267 are referred to.  The Provisional Specification describes the use of oxidizing substances in general such as chromates, manganates, peroxides such as lead peroxide and nitrophenol and in example (1) the sodium nitrite may be replaced by potassium permanganate, lead peroxide, or sodium chromate.ALSO:Rape seed oil, linseed oil, acids thereof or other drying oil is heated with aqueous caustic soda sulphur and sodium nitrite to prepare a factice.