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Minisci showed that C5-C7 methyl esters, 1-chloroalkanes, and amines are chlorinated by R2NC1 via R2NH • + in 96% H2S04. Fe(II) was used for initiation. This type of chlorination has been extended to alcohols, ethers, carboxylic acids, and amides using light in place of Fe(II) for initiation. These chlorinations are of unusual synthetic importance because (1) selectivity for the -1 position in C6 and C8 substrates is 90-92% in most cases, (2) selectivity for monochlorination is 90% with less than 5% polychloro products at 90% monochlorination, (3) alcohol and ether groups are totally protected from oxidation by protonation, (4) reactions are photochemical with exceptionally high quantum yields, (5) yields based on R2NC1 are 60-80%, and (6) the reactions offer a solution to the problem of converting monofunctional compounds to difunctional species in which the functional groups are widely separated.The Hofmann-Loffler reaction is exemplified by eq 1.The mechanism has been established as proceeding via nitrogen cation radicals.3-5 The extension to intermolecular chlorinations was first reported in a series of papers by Minisci.6 Methyl esters of C5-C7 acids,6 1-

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