Sulphuryl chloride, reaction

Dangerous materials may require special equipment. Chlorination with gaseous chlorine requires quite expensive storage facilities. Chlorination with chlorine, thionyl chloride, sulphuryl chloride, phosphorus oxychloride, phosphorus trichloride, or phosphorus pentachloride, all of which are fairly hazardous, requires off-gas treatment. Some of these reactants can be recycled. Pyrophoric solids such as hydrogenation catalysts, anhydrous aluminium trichloride for Friedel-Crafts reactions, or hydrides used as reducing agents should usually be handled using special facilities. Therefore, all of the above proce.sses are usually carried out in dedicated plants. 

A mixture of sulphuryl chloride and diethyl ether gives rise to a very violent reaction and significant release of hydrogen chloride, probably as follows ... 

When there is no diluent, organic acid chlorides and metal halides react very violently with DMSO. This goes for acetyl chloride, benzenesulphonyl (C6H5SO2CI), cyanuryl chloride, phosphorus and phosphoryl trichlorides, tetrachlorosilane, sulphur, thionyl, and sulphuryl chlorides. With oxalyl chloride, the reaction is explosive at ambient temperature, but can be controlled at -60°C in a solution with dichloromethane. The dangerous reactions are thought to be... 

From phosphorus trichloride, benzyl alcohol and 2 mol. of a tertiary base, dibenzyl hydrogen phosphite (XIV), is obtained which on treatment with chlorine or a chlorinating agent (e.g. sulphuryl chloride)4 gives the phosphorochloridate (XV). Although not isolated, (XV) is almost certainly obtained by treatment of (XIV) with a polyhalogen hydrocarbon because reaction in the presence of an alcohol or of a primary or secondary amine gives a triester (XVI) or a phosphoramidate. 

J. M. Ballard, L. Hough, and A. C. Richardson, Reaction of sucrose with sulphuryl chloride, J. Chem. Soc. Chem. Commun. (1972) 1097-1098. 

L. Hough, A. C. Richardson, and M. A. Salam, Reaction of raffinose with sulphuryl chloride, Carbohydr. Res.,11 (1979) 85-93. 

Method 2. In a 500-ml. round-bottomed flask, fitted with an efficient reflux condenser, place 92 g. (106 ml.) of toluene, 68 g. (41 ml.) of redistilled sulphuryl chloride and 1 g. of dibenzoyl peroxide (Section IV,196). Reflux gently, when a vigorous reaction takes place the reaction is complete in 30 minutes. Isolate the benzyl chloride as described in Method 1. The yield is 50 g. 

Peroxides react vigorously with thionyl chloride, forming sulphuryl chloride. The metal remains either as chloride or as a mixture of chloride and sulphate, according to the proportion of thionyl chloride. With thionyl chloride in excess the reaction takes place according to the equation (using barium peroxide) ... 

Pure sulphuric acid gradually yields chlorosulphonic acid and pyro-sulphuryl chloride by concurrent independent reactions on treatment with thionyl chloride.8 Nitric acid vigorously oxidises thionyl chloride to sulphuric acid, probably with intermediate formation of iii tryl chloride,... 

Bone charcoal or activated wood charcoal is a convenient accelerator, combination occurring instantly. If the vessel in which the reaction is carried out is cooled to 30° C., the sulphuryl chloride is condensed and may be drained away as rapidly as it is formed.8 The terpene... 

Chemical Properties.—At a dull red heat sulphuryl chloride vapour is completely decomposed into sulphur dioxide and chlorine. At 320° C. the reaction appears to be of the first order, proceeding entirely in the gas phase at lower temperatures, however, reaction takes place on the wall of the containing vessel.2... 

At 200° C. sulphuryl chloride converts sulphur into monochloride, this result probably being preceded by dissociation of the sulphuryl chloride into chlorine and sulphur dioxide. In the presence of aluminium chloride this reaction can be effected even at the ordinary temperature, and aluminium chloride is known to favour the dissociation of sulphuryl chloride ... 

The chloride has no action on selenium dioxide even at high temperatures or under great pressure.2 Sulphuryl chloride reacts with tellurium with the sulphuryl chloride in excess the reaction is ... 

The reaction between sulphuryl chloride and ammonia is complex, various products being obtained under different conditions the products include iminosulphamide, NII2.S02.NII.S02.NII2, which behaves as a monobasic acid, trisulphimide and sulphomelide, both acidic substances of composition (S02.NH)3, and sulphamidc, S02(NII2)2, which is also acidic.3... 

Like sulphuryl chloride, pyrosulphuryl chloride can convert many elements, e.g. sulphur, phosphorus, antimony and mercury, into the corresponding chlorides, with simultaneous formation of sulphur dioxide and trioxide.2 In the reaction between pyrosulphuryl chloride and phosphorus pentachloride or trichloride, there are obtained phosphorus oxychloride, sulphur dioxide and chlorine. 

The following methods are available for the preparation of chloro-sulphonic acid (1) The substance can be obtained by the gradual action of moisture (e.g. atmospheric moisture) on sulphuryl chloride a similar reaction occurs with sulphuric acid and is more easily regulated ... 

At the ordinary temperature chlorosulphonic acid dissolves sodium chloride, displacing hydrogen chloride and forming sodium chloro-sulphonate,11 this reaction being due to its acidic nature. It is of interest that ammonium chlorosulphonate can be synthesised by the action of sulphuryl chloride on aminosulphonic acid at 100° C.12... 

The remaining compounds of bromine and all those of iodine corresponding with thionyl and sulphuryl chlorides and chloros ulphonic acid are cither unknown or their existence is very doubtful. There is no reaction between sulphur dioxide and bromine analogous to that by which sulphuryl chloride is formed from sulphur dioxide and chlorine this is true between 100° and 200° C., both in the dark and under strong illumination, also in the presence of likely catalysts.2... 

Especially interesting from the evidence which it supplies as to the possibility of a bimolecular structure for sulphur trioxide is the formation of this substance when sulphuryl chloride and silver sulphate are heated together.8 This reaction would be expected to follow the course... 

Another method of preparation for pure sulphamide is to dissolve the product of the reaction between sulphuryl chloride and liquid ammonia in a small quantity of water and acidify the solution in order to cause hydrolysis. After two or three days, when hydrolysis is complete, the mixture is evaporated to dryness in vacuo and the residue extracted with ethyl acetate. The sulphamide is dissolved out and on evaporating off the ethyl acetate, pure sulphamide is obtained.3... 

Pyrosulphuryl chloride, sulphuryl chloride, thionyl chloride and sulphur monochloride all convert tellurium into the tetrachloride, the reaction proceeding most readily with the last named. In the case of thionyl chloride and sulphur monochloride the product is tellurium dichloride if the tellurium is present in excess.3 With pyrosulphuryl chloride the compound formed is TeCl4.SOs when this is acted upon by dry ammonia the product contains tellurium nitride.4... 

Many examples of this type of reaction are known the decomposition of arsine the decomposition of phosphine on surfaces of glass, f porcelain, J silica the decomposition of formic acid vapour on a variety of different surfaces— glass, platinum, rhodium, titanium oxide, and others the decomposition of nitrous oxide on the surface of gold Tf the decomposition of sulphuryl chloride on the surface of glass the decomposition of hydrogen iodide on the surface of platinum ff the decomposition of hydrogen selenide on the surface of selenium. J J A general discussion... 

The vanadium tetrachloride distils over and is purified from any ferric chloride present either by distillation or by extraction of the product with carbon tetrachloride, in which only the vanadium halide is soluble.2 Sulphuryl chloride, thionyl chloride, sulphur monochloride, and phosgene can all be used in the last reaction instead of chlorine, and the ferrovanadium also can be substituted by vanadium carbide, V4C3,3 nitride, VN,4 subsilicide, V2Si,5 disilicide, VSi2,8 or pentoxide.7... 

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