High Energy Halogen Chemistry.

Dichlorine heptoxide was shown to be a versatile perchlorylating reagent. Reaction with alcohols provides a general method of synthesizing alkyl perchlorates, including electronegatively substituted examples, such as 2-fluoro-2,2-dinitroethyl perchlorate and 2,2-dinitropropyl perchlorate. Secondary amines gave dialkylperchlorylamines, and primary amines gave alkylperchlorylamines, a new class of compounds. The latter gave alkali salts stable in aqueous solution. Ketones gave gem-diperchlorates. Nitronate salts gave oxidative coupling, chlorination and Nef reaction products. Unsuccessful attempts were made to prepare perchlorylalkanes from silver chlorate and alkyl halides. Bis2-fluoro-2,2-dinitromethylmercury reacted with methyl iodide to give 1-fluoro-1,1-dinitroethane. Perchloryl fluoride reacted with 2-fluoro-2,2-dinitroethanol gave 2-fluoro-2,2-dinitroethyl methyl ether. Author