Sulphur dichloride, reaction

By the reaction of sulphur dichloride oxide with the hydrated chloride ... 

Nickel forms yellow anhydrous halides NiXjlX = F. Cl. Br) and a black iodide Nil2 all these halides are made by direct combination of the elements, and the chloride by reaction of sulphur dichloride oxide with the hydrated salt. All dissolve in water to give green solutions from which the hydrates can be crystallised the solutions contain the ion [NifHjOls], and the chloride crystallises as NiCl2.6H2O, nickel(II) chloride hexahydrate. 

Acetone is used. However, if sulphur dichloride in excess is present in too large quantities, the reaction becomes particularly dangerous. 

In its action on organo-magnesium compounds,3 sulphur tetrachloride behaves as if it consists only of sulphur dichloride and chlorine, and its reactions with sulphur trioxide (see before) appear to be capable of a similar interpretation in these cases it is indeed possible that sulphur dichloride and chlorine, present as products of dissociation, are the actual agents in the chemical change. 

By the action of chlorine and chlorine compounds on the sulphides of arsenic. By passing chlorine over the dry sulphides, realgar or orpiment, at 130° to 140° ., theoretical yields of arsenic trichloride and of sulphur dichloride are obtained.5 The trisulphide reacts with hydrogen chloride in the cold, but chlorination by means of hydrochloric acid is difficult, only a small quantity of the chloride being volatilised.7 The reaction is facilitated by the presence of ferric chloride,8 cuprous chloride or potassium antimonyl tartrate.9 Other chlorinating agents, effective with the sulphides, are sulphur mono-chloride,10 a mixture of ammonium chloride and nitrate,11 and mercuric chloride.12... 

With Sulphur Chloride. The action of sulphur chloride on dichloroethyl sulphide has been studied by Gibson, Mann and Pope. It has been shown that the result of the reaction between these two compounds is different according to whether the sulphide reacts with sulphur monochloride or with sulphur dichloride. 

Sulphur dichloride on the contrary reacts vigorously with dichloroethyl sulphide even at 0° C. The reaction may become violent according to the ratio of dichloroethyl sulphide to sulphur dichloride and heat is always developed. The products vary according to the relative quantities of the two reactants. If the dichloroethyl sulphide is in excess, the compound Cl—S—CHj—CHj—Cl is formed ... 

Several methods for the preparation of CF3SSC1, chloro(trifluoromethyl)-disulphane, have been reported.73 Under photolytic conditions, bis(tri-fluoromethyl)disulphane reacts with either sulphur dichloride or dichlorodi-sulphane to produce small quantities of CF3SSC1. The former reaction appears to proceed via formation of S2C12, accompanied by large amounts of CF3SC1 as a by-product. The reaction of trifluoromethanethiol with sulphur dichloride at ambient temperatures is probably the best method, giving yields of the disulphane between 60 and 70% ... 

The WiUgerodt reaction has been applied to 2-propionylxanthone to give xanthon-2-ylpropionic acid/ A new type of functional group, the a-chlorothiosulphenyl function, has been produced at the 9-position by the reaction of sulphur dichloride with xanthione (212). The new compound (214), which has five adjacent electrophilic sites, may be in equilibrium with the ionic form (213), which is formed from xanthione and sulphur dichloride-tin(iv) chloride. 

In the phenylthio series, 4-alkylphenols are widely used to produce the so-called thio bisphenols, the higher alkyl members of which are important industriai chemicals discussed further in Chapter 13. For 4-methylphenol and such higher members, Lewis acids are generally employed and milder conditions with sulphur dichloride. Thus, a mixture of 4-methylphenol in hexane containing a small proportion of zinc chloride was kept at 0-10 C during the addition of sulphur dichloride in 1 hour. Reaction was continued for 2 hour and the product... 

Bis-phenol monosulphides and disulphides resulting from the reaction of 4-alkylphenols writh sulphur monochloride and with sulphur dichloride are of importance in the form of their calcium, barium, magnesium salts as lubricating oil additives although their place has been partly displaced by the alkoxyphosphorodithioates. Thus 4-tert-nonylphenol and 4-tert-octylphenol, afford 2,2 -thiobis products (R = t-CgHig and t-CgHi repectively (ref. 82). 

Sulphur dichloride combines with phosphorotetrathioic acid with the elimination of hydrogen chloride (4.85). Further reaction of the remaining SH groups enables three-dimensional networks of general composition (PS) to be built up (Table 4.16). 

Various derivatives of sulphur may be prepared by the reaction of sulphur monochloride, sulphur dichloride or sulphenyl halides with thiolates the products depend on the reactant stoichiometry. 

Very recently a gap has been filled by the preparation of the sulphur compound (58 X = O), obtained by the action of sulphur dichloride on dimedone dioxime. A minor product isolated from the same reaction appears to be the related structure (58 X = S). 

Appearance white crystalline powder resulting from the reaction of 2,4-dichlorophenol with sulphur dichloride in the presence of AICI3... 

Mustard was also produced by the reaction of ethene with sulphur dichloride (SCI2). The process took place in a solvent, which sometimes had to be removed from the reaction mixture at the end of the process, but did not produce sulphur as a by-product. 

A somewhat similar reaction is the power of sulphur oxide dichloride to remove water of crystallisation from hydrated chlorides, the hydroxyl groups of the water molecule reacting as do those in the acid molecules in the above reaction. 

In both reactions above, the oxide dichloride is refluxed with the acid or the hydrated chloride the sulphur dioxide and hydrogen chloride pass off and any unused sulphur oxide dichloride is distilled off in vacuo. 

Prepare a saturated solution of sodium sulphide, preferably from the fused technical sodium polysulphide, and saturate it with sulphur the sulphur content should approximate to that of sodium tetrasulphide. To 50 ml. of the saturated sodium tetrasulphide solution contained in a 500 ml. round-bottomed flask provided with a reflux condenser, add 12 -5 ml. of ethylene dichloride, followed by 1 g. of magnesium oxide to act as catalyst. Heat the mixture until the ethylene dichloride commences to reflux and remove the flame. An exothermic reaction sets in and small particles of Thiokol are formed at the interface between the tetrasulphide solution and the ethylene chloride these float to the surface, agglomerate, and then sink to the bottom of the flask. Decant the hquid, and wash the sohd several times with water. Remove the Thiokol with forceps or tongs and test its rubber-like properties (stretching, etc.). 

Toluene, the major solvent, was stirred for three days with several portions of sulphuric acid, washed, dried, and stored over calcium hydride on a vacuum rack. The toluene was distilled out immediately prior to the reaction. The dichlorides were vacuum distilled at the time of the reaction into three fractions, and the middle fraction, about 60% of the total, used. The dichlorides were obtained from Petrach, stored in a nitrogen glove bag and handled by syringe. 

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