Hofmann-Martius reaction

When HCl salts of arylalkylamines are heated at 200-300°C, migration occurs. This is called the Hofmann-Martius reaction. It is an intermolecular reaction, since crossing is found. For example, methylanilinium bromide gave not only the normal products o- and p-toluidine but also aniline and di- and trimethylanilines." As would be expected for an intermolecular process, there is isomerization when R is primary. 

The API bumetanide reacts under acidic conditions to the convert the secondary amine into the corresponding primary amine (Fig. 41) (62). The mechanism is analogous to the Hofmann-Martius reaction resulting in the debutylated amine and z-butyl chloride (the chloride presumably comes from HC1) (63). 

Reilly-Hicldnbottom rearrangement is a variation of the Hofmann-Martius reaction in which a Lewis acid is used instead of a protic acid. The reaction follows an analogous pathway ... 

V-Alkylaniline and /V,/V-di alkyl aniline hydrochlorides can be rearranged to C-alkyl anilines by heating the salts to 200—300°C. In this reaction, known as the Hofmann-Martius rearrangement, the alkyl group preferentially migrates to the para position. If this position is occupied, the ortho position is alkylated. 

Hofmann Degradation Hofmann Isonitrile Synthesis Hofmann Reaction Hofmann-Loffler-Freytag Reaction Hofmann-Martius Rearrangement Hofmann-Sand Reactions Hooker Reaction Homer Reaction... 

Hofmann-Leffler reaction 656 Hofmann-Martius rearrangement 635 TT-complex mechanism 636 Hofmann rearrangement 628... 

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