Chlorine, reaction with hydrogen phosphorus trichloride

Bischloromethyl ether has been prepared by saturation of formalin with dry hydrogen chloride by the reaction of paraformaldehyde with phosphorus trichloride or phosphorus oxychloride, by solution of paraformaldehyde in concentrated sulfuric acid and treatment with ammonium chloride or dry hydrogen chloride, and by suspension of paraformaldehyde in seventy or eighty percent sulfuric acid and treatment with chlorosulfonic acid. It is formed together with the asymmetrical isomer when methyl ether is chlorinated and when paraformaldehyde is treated with chlorosulfonic acid. The present method has been published. ... 

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. 

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. 

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