Phosphorus -sulfide

Table 6. Products from Hydrolysis of Phosphorus Sulfides,...

A dry 1-L, three-necked, round-bottomed flask, fitted with a reflux condenser, mechanical stirrer, and ground-glass stopper, is charged with 111.0 g (0.25 mol) of phosphorus sulfide, P4S10 (Note 1) and 270 g (2.5 mol) of anisole (Note 1). Stirring Is commenced and the mixture is heated at reflux temperature by use of a heating mantle. After 1 hr, the solution Is... 

Commercial phosphorus sulfide, 45 0, is used without purification. Checkers used P4S10 from Matheson, Coleman and Bell and from Alfa Products, Morton/Thiokol, Inc. Best results (yield, melting point) were obtained with the Alfa sample, mp 291-295°C. 

When heated with sulfur, PH3 yields H2S and a mixture of phosphorus sulfides. Probably the most important reaetion industrially is... 

Figure 12.1S Structures of phosphorus sulfides and oxosulfides (schematic). Table 12.6 Physical properties of some phosphorus sulfides...

Phosphorus sulfides Phosphorus chlorides Organic P compounds... 

Phosphor-stahl, tn. phosphoriis steel, -stange, /. stick of phosphorus, -sulfid, n. (any) phos-phoriis sulfide. 

Schwefel-natrium, -natron, n. sodium sulfide, -nickel, m. nickel sulfide, -niederschlag, m. precipitate of sulfur, precipitated sulfur, -ofen, m. sulfur burner, -oxyd, n. (any) sulfur oxide, -phosphor, m. (any) phosphorus sulfide, -probe, /. sulfur sample mercury sulfide, -quelle, /. sulfur spring, -rducherung, /. sulfur fumigation, -rubin, m. ruby sulfur, realgar, -salz, n. sulfur salt, thio salt, sulfo salt sulfate. 

Carius (8) replaced the oxygen in phosphoryl chloride by sulfur. This may be somewhat analogous to the replacement of oxygen in a carbonyl group by sulfur using phosphorus pentasulfide. Prinz (8) used thionyl chloride in his reaction with phosphorus sulfide and De Fazi (2) used carbon tetrachloride in a very interesting preparation of this important intermediate. 

Both XIV and XV are highly reactive and neither can be isolated from the reaction mixture in the absence of F,t2NH however, upon reaction with elemental sulfur, conversion to the phosphorus sulfide analogs (XVI and XVII) occurs. The latter are crystalline solids stable indefinitely at 25°C in the absence of Et2NH. 

In manufacture of Malathion, the phosphorus sulfide dissolved in toluene is treated first with methanol, then diethyl maleate. Use of insufficient toluene to dissolve the sulfide led to a runaway exothermic reaction and explosion. 

Figure 2 Structures of some phosphorus sulfide molecules...

Table 1 Phosphorus sulfides and structurally analogous group 15 chalcogenides...

Several of these phosphorus sulfides are produced commercially for industrial applications. P4S3 is one of the key chemical constituents of strike-anywhere matches and has been used industrially for this purpose ever since 1898. P4S10 is the most widely industrially used of the phosphorus sulfides with applications in the preparation of lubricant additives and pesticides and in organic chemistry to convert carbonyl or alcohol groups into their sulfur analogues (see Section 5.4). 

Synonyms Phosphorus sulfide phosphorus persulfide phosphorus sulfide, thiophosphoric anhydride... 

The oxidation of phosphorus by elemental sulfur to give binary phosphorus sulfides, which is initiated by mild heating (<100 °C) or upon photolysis at 0 °C, may involve the formation of the catenaS biradical in the rate-determining first step. ... 

The chemistry of phosphorus and sulfur is considerably more complicated than phosphorus-oxygen chemistry.)13 Only two phosphorus sulfides. P4SinaiK) P4S, are isoelectronic and isostruclural with phosphorus oxides. The former may be prepared by allowing stoichiometric amounts of phosphorus and sulfur to react ... 

Two cage phosphorus sulfides may be synthesized by the formation of sulfide bridges through the action of bisririmethyltin) sulfide.1 ... 

Ring closure of 1,4-dicarbonyl compounds with phosphorus sulfides (Paal synthesis) 884... 

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