Hofmann's Rule

Hofmann's Rule implies that steric effects have the greatest influence on the outcome of the Hofmann or similar eliminations. The loss of the β-hydrogen occurs preferably from the most unhindered (least substituted) position [-CH₃ > -CH₂-R > -CH(R₂)]. The product alkene with fewer substitutents will predominate.

Ester Pyrolysis also obeys this preference, and the Hofmann Rule is generally followed whenever a reaction passes through a cyclic transition state.

Hofmann's Rule is valid for all intramolecular eliminations and for the Hofmann Elimination. Most bimolecular eliminations will follow Saytzeff's Rule.