The Hofmann rearrangement is an organic reaction used to convert a primary amide to a primary amine using a halogen, base, water, and heat. The reaction. Hoffmann Rearrangement. Dima Berbasov. May, 1 August Wilhelm von Hofmann Hofmann was the first to introduce molecular. Hofmann. The classical Hofmann rearrangement is the conver- sion of a primary carboxamide to a primary amine using aqueous NaOH and Br In order to improve the.


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The reaction begins with deprotonation of the amide by the base to form an anion which then hofmann rearrangement the halogen to form a N-haloamide.

The Hofmann and Curtius Rearrangements — Master Organic Chemistry

The key observation to hofmann rearrangement in both cases is that the C1-C2 bond has broken, and a new C2-N bond has formed. Transformations of the isocyanate Part 1: Prelude The Hofmann rearrangement occurs with an amide.


The Curtius rearrangement occurs with an acyl azide. Both are hofmann rearrangement prepared from acyl halides through an addition-elimination reaction.

The acyl halides can be prepared from carboxylic acids through using hofmann rearrangement reagent like thionyl chloride SOCl2 or phosphorus pentachloride PCl5. This results in hofmann rearrangement breakage of N-H and the formation of N-Br, resulting in the installation of a good leaving group on the nitrogen.

Hofmann rearrangement - Chemistry LibreTexts

The hofmann rearrangement step in the Hofmann and Curtius rearrangments is migration of a carbon atom to displace hofmann rearrangement leaving group on an adjacent nitrogen.

This requires two curved arrows to draw, which are shown in the structure on the far left below. In the first curved arrow, the C-C bond breaks, and a new C-N bond forms. In the second curved arrow, the N—LG leaving group bond breaks.

Countless points are needlessly lost in exams every year by students who get the curved hofmann rearrangement right but end up drawing the wrong structure! At first this rearrangement probably looks… odd.

Hofmann rearrangement

Just another example of how things you learn in an earlier part of organic chemistry can come back in a later part of the course!

In the Curtius, heating the acyl azide results in rearrangement. The leaving group is nitrogen gas N2. A subtle difference between the Curtius and the Hofmann is that there is no hydrogen attached to N in the Curtius, so we end up with a negative charge on the nitrogen in the rearranged hofmann rearrangement.

Formation of the Isocyanate The next step is going from our rearranged species to the isocyanate.

Hofmann rearrangement - Wikipedia

But for our teaching purposes, I think hofmann rearrangement helps to treat this step in isolation. Several reagents can substitute for bromine. Sodium hypochlorite[4] Lead tetraacetate[5] N-bromosuccinimidebis trifluoroacetoxy iodo benzene[6] and 1,8-diazabicyclo[5.

In the following example, the intermediate isocyanate is trapped by methanolforming a carbamate. In a similar fashion, the intermediate isocyanate can be trapped by tert-butyl hofmann rearrangementyielding the tert-butoxycarbonyl Boc -protected amine.