Hypochlorites, alkyl sodium, with amines

Ortho-Alkylation of aromatic amines. OassmanamlGnietzmacher have described a simple, high-yield procedure for specific orr/io-mcthylation of anilines. The aniline (1) is treated with 1 eq. of/-butyl hypochlorite (1,90 2,50 3, 38) or ofN-chlorosuceini-mide(l, 139 2,69- 70 3, 36,142) in methylene chloride at -65°. Then dimethyl sulfide (3 eq.) is added at the same temperature. After 40 min, sodium mcthoxide (1.2 eq.) in... 

Treatment with sodium hypochlorite or hypobromite converts primary amines into N-halo- or N,N-dihaloamines. Secondary amines can be converted to N-halo secondary amines. Similar reactions can be carried out on unsubstituted and N-substituted amides and on sulfonamides. With unsubstituted amides the N-halo-gen product is seldom isolated but usually rearranges (see 18-13) however, N-halo-N-alkyl amides and N-halo imides are quite stable. The important reagent NBS is made in this manner. N-Halogenation has also been accomplished with other reagents, (e.g., sodium bromite NaBr02) benzyltrimethylammonium tribromide (PhCH2NMe3 Br3"), and NCS. The mechanisms of these reactions involve attack by a positive halogen and are probably similar to those of 12-47 and 12-49.N-Fluorination can be accomplished by direct treatment of amines °° or... 

It is well-known that organoboranes can be utilized to yield primary amines by treating them with chloramine or hydroxylamine-O-sulfonic acid Recently Kabalka et al. reported a convenient synthesis of primary alkyl amines via the reaction of organoboranes with ammonium hydroxide in the presence of sodium hypochlorite (Eq. 13) The reaction presumably proceeds through the in situ formation of chloramine. 

Hofmann established a route to higher homologues of aromatic amines by intramolecular rearrangement of /V-alkylated anilines, a reaction that was of great theoretical and technical importance. In 1870, he reported the conversion of an acid amide into an amine, with loss of one carbon. In 1881, he discovered that when the degradation was carried out with sodium hypochlorite or hypobromite, the yields of primary amines were excellent. This is the Hofmann degradation, or reaction, that takes place via formation of isocyanate60. 

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