Phosphorus disulphide

Phosphorus(III) oxide dissolves in several organic solvents, for example benzene, carbon disulphide the molecular weight in these solvents corresponds to the formula P40(, as does the density of the vapour, and the structure is ... 

Industrially, chlorine is obtained as a by-product in the electrolytic conversion of salt to sodium hydroxide. Hazardous reactions have occuned between chlorine and a variety of chemicals including acetylene, alcohols, aluminium, ammonia, benzene, carbon disulphide, diethyl ether, diethyl zinc, fluorine, hydrocarbons, hydrogen, ferric chloride, metal hydrides, non-metals such as boron and phosphorus, rubber, and steel. 

The reaction of a-aminonitriles and carbon disulphide was stated by Cook and Heilbron to give 5-amino-2-mercaptothiazoles however, they later found that the same reaction with aminoacetonitrile was more complex. When aminoacetonitrile sulphate in ethanolic solution was treated with carbon disulphide, the dithiodicarbamate 9 was formed. Benzylation was then carried out treatment of the resulting ester 10 with phosphorus tribromide with subsequent loss of water gave 5-amino-2-benzylthiothiazole 11 in a quantitative fashion. The rapid reaction was thought to be the first example of the formation of a 5-aminothiazole from an a-aminoamide. 

The spore coats make up a major portion of the spore, consisting mainly of protein with smaller amounts of complex carbohydrates and Bpid and possibly large amounts of phosphorus. The outer spore coat contains the alkali-resistant protein fraction and is associated with the presence of disulphide-rich bonds. The alkali-soluble fraction is... 

Reaction of perthiophosphonic anhydrides (64) with amines leads first to (105) and then, by further attack, to (106). With ammonia itself the second addition proceeds at the same phosphorus atom as the initial attack, giving (107) and (108). The anhydride (64) is also reported to react with 1,3-dioIs to give cyclic phosphonyl disulphides (109). Thermal decomposition of phenylphosphinic anhydride (110) may lead to the formation of PhP since in the presence of benzil the formation of the phosphorane (111) was observed. ... 

With phosphorus trichloride, a rather complex reaction results partly in the formation of [PhaP N uPPha PPhCl]+ Cl. The reactivity of the phosphorus(iii) atom is also demonstrated by its ability to desulphurize thiophosphoryl chloride, and its ready reactions with Group VI elements, diborane, and carbon disulphide ... 

Phosphinyl radicals, obtained by hydrogen abstraction from dialkyl phosphites, have been trapped with t-nitrosobutane and the resultant nitroxyl radicals examined by e.s.r, The reaction of phosphinyl radicals, e.g. (5) and (6), with olefins has been shown to occur with retention of configuration at phosphorus. " These radicals have also been postulated as intermediates in the reactions of dialkyl disulphides and diaryl disulphides with phosphinates. " From the reaction of diphenyl disulphide... 

The same goes for carbon (the accident was caused because carbon was used instead of manganese dioxide, by mistake), sulphur and phosphorus. There was a detonation with carbon. With phosphorus the detonation occurred once the carbon disulphide used to dissolve phosphorus vapourised red phosphorus behaves the same way. The same happened with the potassium chlor-ate/sodium nitrate/sulphur/carbon mixture, which led to a violent detonation as well as with the potassium perchlorate/aluminium/potassium nitrate/barium nitrate/water mixture. In the last case the explosion took place after an induction period of 24h. 

Sulphur as well as phosphorus gives highly violent reactions when they are heated with potassium. With carbon disulphide, potassium creates a mixture, which detonates on impact. The same happens by heating. With sulphur dioxide, potassium in the molten state combusts. Finally, the potassium/sulphuric acid mixture gives rise to detonations. 

Miscellaneous Reactions.—A full report has appeared of the reactions of carbon dioxide and carbon disulphide with tervalent phosphorus aryl esters and amines the products are ureas and thioureas, respectively.74 The suggested mechanism, previously invoked for similar reactions of carboxylic acids, involves the N-phosphonium salt (97). 

Further use has been made of the reaction of disulphides with tervalent phosphorus compounds in phosphorylation reactions, e.g. in the synthesis of (57).68... 

The desulphurization of disulphides by tervalent phosphorus compounds has been the subject of a review.70 The light-induced desulphurization of benzylic sulphides by phosphites has found further use in the synthesis of cyclophanes which exhibit the formation of intramolecular charge-transfer complexes, e.g. (61) and (62).71... 

To date, however, only few reactions between phosphine and a non-metal halide, in which a chemical bond is formed between phosphorus and a non-metal by HCl condensation, are known. To these, apart from the above-mentioned reactions, belongs also the reaction with CF3SCI which, depending upon the chosen proportions of the reactants, in a sealed tube at -95 °C leads to the formation of (CF3S)2PH or (CF3S)3P Both compounds are not very stable thermally and decompose at 40-50 °C. Tris(trifluoromethylthio)-phosphine forms an unstable adduct with chlorine, which decomposes at 0 °C to give a mixture of PCI3, bis(trifluoromethyl)-disulphide and trifluoromethyl-sulphenyl chloride. 

Mixtures of chlorates with such materials must not be ground together with a postle and mortar. The materials should be ground separately, and then carefully mixed on paper with a feather. Phosphorus in contact with a chlorate may explode spontaneously. Thus if a drop of soln. of phosphorus in carbon disulphide be allowed to fall on a little potassium chlorate, a loud explosion occurs as soon as the carbon disulphide has evaporated. The red phosphorus in the mixture on the side of a box of safety matches gives a series of sparks when a crystal of potassium chlorate is rubbed thereon, and serious accidents have occurred as a result of the accidental rubbing of tabloids of potassium chlorate against the sides of a match-box in the pocket. 

Assemble an apparatus as shown in Fig. 97. Dissolve 10 g of commercial white phosphorus in 50 ml of dry carbon disulphide in flask... 

Preparation of Phosphorus Iodide Pgl. To prepare phosphorus iodide, one must have thoroughly dried carbon disulphide (see Preparation of Phosphonium Iodide ) and purified white phosphorus (see Preparation of Phosphorus Tribromide ). (Perform the experiment in a fume cupboard . ... 

Carbon disulphide is an excellent solvent for fats and resins, - it is employed technically for the extraction of vegetable fats and oils and for removing fats from wool. It dissolves rubber, camphor and other organic substances, as well as iodine, sulphur, phosphorus and aluminium bromide.7... 

The tetrachloride may be purified by recrystallisation from phosphorus oxychloride, from which it separates as cubical crystals. It is practically insoluble in carbon disulphide, which can therefore be used to remove any monochloride present. The heat of formation of the tetrachloride from chlorine and amorphous selenium is 46-1 Calorics 4... 

By the addition of iodine to a solution of phosphorus selenide, P4Se3, in carbon disulphide Mai5 lias obtained as a solid substance, tetraphosphorus di-iodide triselenide, PJ Sej, which on rapid heating melts at 154° to 155° C. 

Phosphorus Monoselenide, P2Se, may be obtained by heating one atomic proportion of selenium with two atomic proportions of phosphorus in a current of hydrogen. It is formed with incandescence as a clear red solid, which is combustible and slightly soluble in carbon disulphide. It is decomposed by boiling alkalis witli liberation of phosphine. With metal selenides it forms double selenides. 

Phosphorus Triselenide or Phosphorous Selenide, P2Se3.— This compound may be obtained by heating together phosphorus and selenium in the requisite atomic proportions. The reaction is accompanied by a great evolution of heat. The product is a ruby-red solid, which is combustible on heating. It is insoluble in carbon disulphide. With metal selenides it forms double selenides of the typeP2Se3.2MSe.2... 

Arsenic exhibits allotropy, which is characteristic of non-metals the usual, more stable, metallic form resembles the typical metals in appearance and in being a fairly good conductor of electricity. Under atmospheric pressure it begins to volatilise at about 450° C. and passes into a vapour containing complex molecules, As4, which at higher temperatures dissociate to As2 this complexity is not unusual in non-metals. The yellow allotrope, which is stable at low temperatures, resembles white phosphorus in being soluble in carbon disulphide—a property which emphasises the non-metallic character of this variety. The reactivity of the allotropes, as in the case of phosphorus, differs considerably. 

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