Fluorine disulphide

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. 

Fluorinated base, -dG residue with a disulphide linker at the exocyclic amino group, RT-room temperature. 

Carbon disulphide vapour mixed with hydrogen and directed on to heated platinum reacts to form carbon and hydrogen sulphide.11 Carbon disulphide inflames in the cold in contact with fluorine, and under varying conditions it reacts with chlorine, bromine and iodine. 

Direct syntheses of fluorocarbon-sulphur compounds from non-fluorinated starting materials are limited, but bis(trifluoromethyl) disulphide may be obtained from carbon... 

It is attacked by fluorine but there is no reaction with dry hydrogen fluoride, and only a slow reaction with hydrofluoric acid. Reaction with chlorine produces molybdenum pentachloride. Heating in hydrogen reduces the disulphide directly to molybdenum metal. 

Fluorine is the most electronegative of all the elements, so that the bonds it forms with most other elements have considerable ionic character. With the exception of the alkali halides most crystalline fluorides have structures different from those of the other halides of the same metal. A number of difluorides and dioxides have the same crystal structure, whereas the corresponding dichlorides, dibromides, and diiodides have in many cases structures similar to those of disulphides, diselenides, and ditellurides. The extreme electronegativity of fluorine enables it to form much stronger hydrogen bonds than any other element, resulting in the abnormal properties of HF as compared with the other acids HX, the much... 

The phosphetan (12) with bis(trifiuoromethyl) peroxide or bis(trifluoro-methyl) disulphide at — 78 °C gave the difluorophosphorane (13). The and n.m.r. spectra at — 100 °C show clearly that the phosphorane is a 2.3 1 equilibrium mixture of (13a) and (13c), equilibration via the high energy phosphorane (13b) being slow at this temperature. The apicophilicity of fluorine is balancing the increased strain involved in placing the four-membered ring diequatorial. 

The compounds of type (6.536) can be prepared quite simply by reacting thiophosphoryl chloride with the appropriate 1-butyl or 1-pentyl Grignard reagent (6.537) and fluorinating the disulphide so obtained (6.538). 

Exothermic secondary reactions occur when the mixture obtained by addition of the disulphide (CFaCl CFa)3S2 (from CFj CF2 + SaCla at 120 °C) to a solution of aziridine in methylene chloride at — 40 °C is evaporated at -10 °C, and the residue is found to contain the triaziridinyletbane (92) and the thiazoline (93). These products are believed to arise via initial stepwise nucleophilic displacement of both fluorines from an ot-CFt group, followed by a final attack by aziridine leading to (92) and CF2CI-CF2 S SH,... 

As mentioned previously (see p. 138), carbon disulphide inserts into the platinum-fluorine bond of [PtF(PPhs)j]+ to give the hydrolytically unstable complex cation (137). ... 

Sulphur.—Compounds Containing Bivalent Sulphur. Attempts to oxidize bistrifluoromethyl sulphide (conveniently prepared by pyrolysis of commercial bistrifiuoromethyl disulphide at 425—435 °C) to either the sulphoxide or the sulphone using the reagents ( i-(n C H4-CO)sOa-100°C, NOjCIO, NOa-u.v., or NOa-Oa-350°C have proved unsuccessful fluorination of the monosulphide with hot argentic or cobaltic fluoride gave trifluoromethyl-sulphur pentafluoride, while bis(trifluoromethyl)sulphur difluoride was formed at low temperatures with fluorine itself. " Bis(trifluoromethyl)-sulphur difluoride and several other bis(perfluoroalkyl)sulphur difluorides, obtained from the corresponding sulphides and chlorine monofluoride (see p. 162), have been converted into bisperfluoroalkyl sulphoxides ... 

Trifluoromethanesulphenyl fluoride, a rare type of compound, has now been obtained in quantitative yield by fluorination of trifluoromethanesulphenyl chloride with mercuric fluoride at 130°C, in vacuo, in platinum or pure nickel apparatus. In the liquid phase the sulphenyl fluoride exists in equilibrium with the dimer CFa-SFj-S-CF, and the mixture of the two slowly disproportionates at room temperature into bistrifluoromethyl disulphide and trifluoiomethylsulphur trifluoride. Trifluoromethanesulphenyl fluoride and its dimer attack magnesium, copper, and mercury to give bistrifluoromethyl disulphide and the corresponding metal fluorides, and etch glass with the formation of bistrifluoromethyl disulphide, trifluoromethane-sulphinyl fluoride, and the thiolsulphonate CFs-SOg-S-CF,. Hydrolysis of the sulphenyl fluoride with moist potassium fluoride also yields the thiolsulphonate ... 

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