Favorskii rearrangement

 Treatment of α-halo ketones possessing at least one α-hydrogen with base in the
presence of a nucleophile (alcohol, amine, or water) results in a skeletal
rearrangement via a cyclopropanone intermediate to give carboxylic acids or
carboxylic acid derivatives (esters or amides). This reaction is known as the Favorskii
rearrangement, and it is widely used for the synthesis of highly branched carboxylic
acids
 α-halo ketones when treated with a strong base (generally
alkoxides)  lead to the formation of esters with rearrangement of
the carbon frame work.
 Mechanism
 The halogen substituent can be a chlorine, bromine or iodine, while the base is usually an alkoxide or
hydroxide. Upon rearrangement, acyclic α -halo ketones give acyclic carboxylic acid derivatives, while cyclic α
-halo ketone substrates undergo a ring-contraction reaction to afford one-carbon smaller cyclic carboxylic acid
derivatives.
 The rearrangement of unsymmetrical α -halo ketones leads to the product, which is formed through the
cleavage of the cyclopropanone intermediate to usually give the thermodynamically more stable of the two
possible carbanions.
 The base attacks the carbonyl carbon resulting in an anion which through phenyl migration forms the anion
of benzylic acid.
 Subsequent acidification can result in the acid itself.
 Initially, the α'-carbon is deprotonated to generate an enolate ion which is followed
by intra molecular nucleophilic substitution to give a cyclopropenone by ring
closure.
 Thus formed cyclopropenone undergoes nucleophilic addition by a base at the
carbonyl carbon which is followed by the cleavage of the CO-Cα bond. Usually the
cleavage occurs so as to give less substituted and more stable carbanion