Disulphide

Carbon Disulphide. This can insert into metal-alkyl and into metal-hydrogen bonds a metal-carbon disulphide 7r-complex is a possible intermediate.  

Isocyanides. Several instances for nickel(ii) and palladium(ii) complexes have been suggested. - One interesting feature is that whereas carbon monoxide only inserts once into a given bond, isocyanides can insert repeatedly, providing a potential route for catalytic polymerisation.  

Cyanides. A qualitative report on insertion of cyanides into diethyl-aluminium compounds has appeared.  

Carbenes,—Attempts to insert Cp2 into several metal-metal bonds failed, because the difluorocarbene precursor MeaSnCCFg) underwent exchange reactions at one of the metals, e.g. 

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Crystalline solid m.p. 35-36 "C, b.p. 154--156 C, prepared by oxidizing A,A -dicycIo-hexylthiourea with HgO in carbon disulphide solution, also obtained from cyclohexylamine and phosgene at elevated temperatures. Used as a mild dehydrating agent, especially in the synthesis of p>eptides from amino-acids. Potent skin irritant. 

HSCH2CH(0H)CH(0H)CH2SH. a useful water soluble reagent for preserving thiols in the reduced state, and for reducing disulphides quantitatively to dithiols. 

Insulin is built up of two polypeptide chains. A of 21 amino-acids and B of 30 amino-acids, linked by two disulphide bridges. 

The base lubricant is usually a petroleum oil while the thickener usually consists of a soap or soap mixture. In addition they may contain small amounts of free alkali, free fatty acid, glycerine, anti-oxidant, extreme-pressure agent, graphite or molybdenum disulphide. 

Crystalline powder, m.p. 174-179 C. Prepared by treatment of thiocarbanilide with sulphur, or by heating aniline, carbon disulphide and nitrobenzene. It is an important rubber accelerator, and on oxidation gives dibenzthiazyl disulphide, also a rubber accelerator. 

CmHizN S, PhNHC(S)NHPh. Colourless flakes m.p. 15rC. Prepared by boiling aniline with carbon disulphide. It is used commercially as a rubber accelerator. 

A pletliora of different SA systems have been reported in tire literature. Examples include organosilanes on hydroxylated surfaces, alkanetliiols on gold, silver, copper and platinum, dialkyl disulphides on gold, alcohols and amines on platinum and carboxyl acids on aluminium oxide and silver. Some examples and references can be found in [123]. More recently also phosphonic and phosphoric esters on aluminium oxides have been reported [124, 125]. Only a small selection out of tliis number of SA systems can be presented here and properties such as kinetics, tliennal, chemical and mechanical stability are briefly presented for alkanetliiols on gold as an example. 

Nuzzo R G and Allara D L 1983 Adsorption of bifunotional organio disulphides on gold surfaoes J. Am. Chem. Soc. 105 4481-3... 

Further reaction then occurs between the disulphur dichloride and the carbon disulphide ... 

This was formerly manufactured by passing sulphur vapour over white hot coal or charcoal. An equilibrium was established and the carbon disulphide vapour was condensed, allowing the reaction to proceed ... 

Carbon disulphide is a volatile, evil-smelling liquid, although if carefully purified, the unpleasant smell is removed, as it is due to impurity. The vapour is inflammable and can form explosive mixtures in air ... 

Carbon disulphide is an excellent solvent for fats, oils, rubber, sulphur, bromine and iodine, and is used industrially as a solvent for extraction. It is also used in the production of viscose silk, when added to wood cellulose impregnated with sodium hydroxide solution, a viscous solution of cellulose xanthate is formed, and this can be extruded through a fine nozzle into acid, which decomposes the xanthate to give a glossy thread of cellulose. 

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 ... 

When sulphur is melted viscosity changes occur as the temperature is raised. These changes are due to the formation of long-chain polymers (in very pure sulphur, chains containing about 100 (X)0 atoms may be formed). The polymeric nature of molten sulphur can be recognised if molten sulphur is poured in a thin stream into cold water, when a plastic rubbery mass known as plastic sulphur is obtained. This is only slightly soluble in carbon disulphide, but on standing it loses its plasticity and reverts to the soluble rhombic form. If certain substances, for example iodine or oxides of arsenic, are incorporated into the plastic sulphur, the rubbery character can be preserved. 

Like bromine, iodine is soluble in organic solvents, for example chloroform, which can be used to extract it from an aqueous solution. The iodine imparts a characteristic purple colour to the organic layer this is used as a test for iodine (p. 349). NB Brown solutions are formed when iodine dissolves in ether, alcohol, and acetone. In chloroform and benzene a purple solution is formed, whilst a violet solution is produced in carbon disulphide and some hydrocarbons. These colours arise due to charge transfer (p. 60) to and from the iodine and the solvent organic molecules. 

Carbon disulphide should never be used if any alternative solvent is available, as it has a dangerously low flash-point, and its vapours form exceedingly explosive mixtures with air. Ether as a solvent for recrystallisation is much safer than carbon disulphide, but again should be avoided whenever possible, partly on account of the danger of fires, and partly because the filtered solution tends to creep up the walls of the containing vessel and there deposit solid matter by complete evaporation instead of preferential crystallisation. 

The crystalline sodium sulphide (NajS,9H20) used to prepare the disulphide is very deliquescent, and only a sample which has been kept in a well-stoppered bottle and therefore reasonably dry should be used. A sample from a badly-stoppered bottle may contain, in addition to the crystals, a certain amount of aqueous solution, in which hydrolysis and partial decomposition will have occurred such a sample should therefore be rejected. Add 4 2 g. of finely powdered sulphur to a solution of 16 g. of the crystalline sodium sulphide in 60 ml. of water, and boil the mixture gently for a few minutes until a clear solution of the disulphide is obtained. 

The most dangerous solvent in the laboratory is carbon disulphide, the flash-point of which is so low that its vapour is ignited, e.g., by a gas-ring 3 4 minutes after the gas has been turned out. CarlK>n disulphide should therefore never be used in the laboratory unless an adequate substitute as a solvent cannot be found. Probably the next most dangerous liquid for general manipulation is ether, which, however, has frequently to be employed. If the precautions described on pp. 79, 163, are always followed, the manipulation of ether should however quite safe. 

Other pairs of liquids which exhibit an upper consolute temperature are methyl alcohol - cyclohexane (C.S.T. 49 -1° critical composition 29 per cent, by weight of methyl alcohol) isopentane - phenol (63 5° 51 per cent, of isopentane) and carbon disulphide - methyl alcohol (40-5° 80 per cent, of carbon disulphide). 

The inflammable solvents most frequently used for reaction media, extraction or recrystallisation are diethyl ether, petroleum ether (b.p. 40-60° and higher ranges), carbon disulphide, acetone, methyl and ethyl alcohols, di-Mo-propyl ether, benzene, and toluene. Special precautions must be taken in handling these (and other equivalent) solvents if the danger of Are is to be more or less completely eliminated. It is advisable to have, if possible, a special bench in the laboratory devoted entirely to the recovery or distillation of these solvents no flames are permitted on this bench. 

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