Phosphorus sulphides

Dry distillation of sodium laevulinate (I) with phosphorus sulphide gives 2-methylthiophene (II) as the main product ... 

Mix intimately in a mortar 100 g. of sodium laevulinate, 250 g. of phosphorus sulphide (1) and 50 g. of clean dry sand. Place the mixture in a flask fitted with a condenser for distillation and a receiver (2). Heat the flask with a free flame until the reaction commences, and then remove the flame. When the reaction subsides, continue the heating until distillation ceases. Wash the distillate with 10 per cent, sodium hydroxide solution to remove acidic by-products and steam distil. Separate the crude 2-methyltliiophene from the steam distillate, dry over anhydrous calcium sulphate, and distil from a little sodium. Collect the pure compound at 113° the yield is 30 g. 

Dimethylthiophene (II) Is re.adily prepared by Interaction of phosphorus sulphide and acetonylacetone (I) ... 

To 125 g. of finely powdered phosphorus sulphide (1) contained in a 500 ml. round-bottomed flask fitted with a reflux condenser, add 60 g. (62 ml.) of redistilled acetonylacetone (2). Heat cautiously at first until... 

Applications of Sulphur.--Much sulphur is consumed in the manufacture of matches, being applied in the form of phosphorus sulphide as a constituent of the heads of common friction matches, whilst on the Continent the wooden splints have frequently been treated with sulphur to facilitate the passage of the flame from the bend to the remainder of the match. Large quantities of sulphur are also required for the production of gunpowder and fireworks for these purposes finely divided sulphur is necessary, but u flowers of sulphur is not suitable on account of its liability to contain tract s of sulphuric acid, due to atmospheric oxidation, which would render its use dangerous. 

Various other processes can be made to yield sulphur monoehloride. The distillation of sulphur with stannous chloride or mercuric, chloride yields sulphur monochloride and, indeed, may be regarded as a modification of the method first given. The action of phosphorus pentacliloridc on sulphur or on metallic sulphides and the action of chlorine on metallic sulphides form closely analogous processes, especially in view of the formation of chlorine as a dissociation product from phosphorus penta-chloride. With phosphorus pentachloride tire phosphorus is found finally as sulphochloride. Of other methods there may be mentioned the interaction of sulphur or of phosphorus sulphide with thionyl chloride,6 and the action of dry chlorine on a hot or boiling solution of... 

This powder takes fire in air at a summer s heat, and burns with a white flame to form phosphoric acid it is violently oxidized and dissolved by nitric acid, forming sulphuric and phosphoric acids it inflames in the vapours of nitrogen peroxide it has no odour when freshly prepared, but after exposure to air, it acquires the smell of hydrogen sulphide it forms a turbid soln. when treated with water, which deposits sulphur and smells of hydrogen sulphide it evolves ammonia when treated with alkali-lye and it is dissolved by hot alkali-lye but not by aq. ammonia or hydrochloric acid. The product is probably a mixture of phosphorus sulphide, and ammonium salts. 

In addition to the numerous compounds reported as a result of the direct union of the elements by fusion, a number have been obtained—by B. Corenwinder, R. Boulouch, A. Seidel, etc.—by crystallization from soln. of phosphorus and sulphur in carbon disulphide. A. Helff said that no compound is formed from soln. of the two elements in carbon disulphide. For A. Delachaux s observations on the production of phosphorus sulphides by the action of hydrogen sulphide or sulphur on phosphine, vide supra.. 

Metallic oxides as well as metals are usually converted into chlorides by the pentachloride, while metallic sulphides usually give the chlorides and phosphorus sulphides. 

Phosphorus combines directly with sulphur in various proportions to give sulphides, the formulae of some of which resemble those of the oxides. It also gives oxysulphides, thiophosphites, thiophosphates and the corresponding acids. The latter salts may be made by the action of alkalies or alkali sulphides on phosphorus sulphides. 

The analogous thioketone already mentioned is obtained in a similar manner from carbon sulphochloride CSCI2, and dimethyl-aniline it may also be obtained by treating the corresponding oxygen ketone with phosphorus sulphide. The two ketones are similar in their reactions [3]. 

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