Acetyl hypochlorite, chlorination

Chloroform can be manufactured from a number of starting materials. Methane, methyl chloride, or methylene chloride can be further chlorinated to chloroform, or carbon tetrachloride can be reduced, ie, hydrodechlorinated, to chloroform. Methane can be oxychlorinated with HCl and oxygen to form a mixture of chlorinated methanes. Many compounds containing either the acetyl (CH CO) or CH2CH(OH) group yield chloroform on reaction with chlorine and alkali or hypochlorite. Methyl chloride chlorination is now the most common commercial method of producing chloroform. Many years ago chloroform was almost exclusively produced from acetone or ethyl alcohol by reaction with chlorine and alkali. 

Sodium salts of fluoroacids react with chlorine fluoride at —112 to —78°C to give explosively unstable fluoroacyl hypochlorites. Trifluoroacetyl hypochlorite and its pentafluoropropionyl, heptafluorobutyryl, difluoroacetyl and chlorodifluo-roacetyl analogues explode without fail if the partial pressure exceeds 27-67 mbar. Hexafluoroglutaiyl dihypochlorite explodes above — 10°C [1]. Of the 4 compounds prepared, acetyl, propionyl, isobutyryl and pivaloyl hypobromites, the 2 latter appeared stable indefinitely at —41°C in the dark, while the 2 former exploded unpredictably as isolated solids [2],... 

CHLORINE OXYGEN ACIDS AND SALTS - DICHLORINE MONOXIDE, HYPOCHLOROUS ACID, AND HYPOCHLORITES] (Vol 5) -as acetylation catalyst [ACETIC ACID AND DERIVATIVES - ACETIC ACID] (Vol 1)... 

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